U.S. patent number 6,559,262 [Application Number 09/669,411] was granted by the patent office on 2003-05-06 for high melting thermoplastic elastomeric alpha-olefin polymers (pre/epe effect) and catalysts therefor.
This patent grant is currently assigned to The Board of Trustees of the Leland Stanford Jr. University. Invention is credited to Larry L. Bendig, Andreas B. Ernst, Raisa Kravchenko, Eric J. Moore, Charles L. Myers, Roger W. Quan, Robert M. Waymouth.
United States Patent |
6,559,262 |
Waymouth , et al. |
May 6, 2003 |
High melting thermoplastic elastomeric alpha-olefin polymers
(PRE/EPE effect) and catalysts therefor
Abstract
This invention relates generally to low ethylene insertions into
I-olefin polymers and processes for production of such polymers
using unbridged fluxional metallocenes, primarily substituted aryl
indenyl metallocenes, and more particularly to use of unbridged,
fluxional, cyclopentadienyl or indenyl metallocene catalyst systems
in methods of production of high melting point I-olefin homo- and
co-polymers, particularly elastomeric crystalline and amorphous
block homo- and co-polymers of I-olefins. The activity of fluxional
unbridged metallocene polymerization catalysts containing at least
one 2-arylindene ligand is increased 10.times. or more by the
addition of small (typically 0.1-10 wt. %) amounts of ethylene to
the polymerization system, which increase is termed the
Polymerization Rate-Enhancement effect (PRE), which is measured in
terms of an Ethylene Enhancement Factor (EEF) as a dimensionless
ratio in the range of from about 1.1 to about 10 or above. The
amount of ethylene included in the reaction system can be selected
and controlled to be so small as to result in essentially minimal
(<2 mole %) incorporation of ethylene units into the resulting
elastomeric polymer and the molecular weight may be increased.
Amounts of ethylene to generate the PRE effect may be greater than
0.1 wt. % and preferably range up to about 2 wt. %. However, if a
polymer with more ethylene is desired, additional ethylene may be
incorporated into the polymerization feed, including up to 10 to
about 50 mole % based on olefin units. A second important aspect of
this invention is the ability to use a PRE activity-enhancing
amount of ethylene in an olefin polymerization without
substantially affecting the physical properties of the elastomer.
In a third important aspect of this invention, I-olefin elastomers
are produced through incorporation of ethylene using unbridged
fluxional catalyst systems which may not otherwise produce
acceptable elastomeric homopolymers. This effect is termed the EPE
effect, for Elastomeric Property-Enhancing effect. The EPE amount
of ethylene required to produce such elastomers typically overlaps
the PRE activity-enhancing amount. Incorporation of up to about 5
mole % or more of ethylene typically will produce an elastomeric
polymer using such catalyst systems. Typical useful amounts of
incorporated ethylene include about 1 to 3 mole %. Preferred
polymers of this invention retain sufficient crystallinity to
provide a high melting point (by DSC) of about 80.degree. C.,
preferably above 100.degree. C., including in the range of from
about 120.degree. C. to about 140.degree. C. and above. Novel
flexible .alpha.-olefin homo and copolymers having elongation in
excess of 600% and substantially no retained force are
disclosed.
Inventors: |
Waymouth; Robert M. (Palo Alto,
CA), Kravchenko; Raisa (Wilmington, DE), Bendig; Larry
L. (Aurora, IL), Moore; Eric J. (Carol Stream, IL),
Myers; Charles L. (Palatine, IL), Quan; Roger W. (Vernon
Hills, IL), Ernst; Andreas B. (Naperville, IL) |
Assignee: |
The Board of Trustees of the Leland
Stanford Jr. University (Stanford, CA)
|
Family
ID: |
27535109 |
Appl.
No.: |
09/669,411 |
Filed: |
September 25, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
097234 |
Jun 12, 1998 |
6160064 |
Dec 12, 2000 |
|
|
Current U.S.
Class: |
526/348;
526/160 |
Current CPC
Class: |
C08F
10/00 (20130101); C08F 210/16 (20130101); C08F
10/00 (20130101); C08F 4/65925 (20130101); C08F
210/16 (20130101); C08F 4/63925 (20130101); C08F
4/63912 (20130101); C08F 4/65912 (20130101); C08F
110/02 (20130101); C08F 110/06 (20130101); C08F
210/06 (20130101); C08F 110/02 (20130101); C08F
2500/01 (20130101); C08F 110/06 (20130101); C08F
2500/20 (20130101); C08F 110/06 (20130101); C08F
2500/12 (20130101); C08F 210/06 (20130101); C08F
210/16 (20130101); C08F 2500/20 (20130101); C08F
2500/03 (20130101); C08F 2500/06 (20130101); C08F
210/06 (20130101); C08F 210/16 (20130101); C08F
2500/04 (20130101); C08F 210/06 (20130101); C08F
210/16 (20130101); C08F 2500/12 (20130101); C08F
2500/03 (20130101); C08F 210/16 (20130101); C08F
210/06 (20130101); C08F 2500/20 (20130101); C08F
2500/06 (20130101); C08F 210/16 (20130101); C08F
210/14 (20130101); C08F 2500/20 (20130101); C08F
2500/03 (20130101); C08F 2500/06 (20130101); Y10S
526/943 (20130101) |
Current International
Class: |
C08F
210/00 (20060101); C08F 10/00 (20060101); C08F
210/16 (20060101); C08F 110/00 (20060101); C08F
210/06 (20060101); C08F 110/06 (20060101); C08F
4/00 (20060101); C08F 110/02 (20060101); C08F
4/639 (20060101); C08F 4/659 (20060101); C08F
210/02 (); C08F 210/16 () |
Field of
Search: |
;526/348,160 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Quirk, Roderic P., Transition Metal Catalyzed Polymerizations,
1988, Cambridge University Press, Cambridge, pp. 719-728. .
Spitz, R., et al., Propene Polymerization with MgCl.sub.2 supported
Ziegler catalysts: Activation by hydrogen and ethylene, 1988,
Makromol. Chem. 189, pp. 1043-1050. .
Valvassori, A., et al., Kinetics of the Ethylene-Propylen
Copolymerization, 1963, Makromol. Chem. 161, pp. 46-62. .
Brintzinger, H, et al., Stereospecific Olefin Polymerization with
Chiral Metallocene Catalysts, 1995, Angew. Chem Int. Ed. Engl. 34,
pp. 1143-1170. .
Pasquet, v., and Spitz, R., Irreversible activation effects in
ethylene polymerization, 1993, Makromol. Chem. 194, pp. 451-461.
.
Busico, V., et al., Siegler-Natta oligomerization of 1-alkenes: a
catalyst's "fingerprint", 2, Preliminary results of propene
hydrooligomerization in the presence of the homogeneous isospecific
catalyst system rac-(EBI) ZrCl.sub.2 /MAO, 1993, Makromol. Chem. ,
Rapid Commun. 14, pp. 97-103. .
Herfert, N., et al., Elementary processes of the Xiegler catalysis,
7, Ethylene, .beta.-olefin and norbornene copolymerization with the
stereorigid catalyst stems iPr[FluCp]ZrCl.sub.2 /MAO, 1993,
Makromol. Chem. 194, pp. 3167-3182. .
Koivumaki, J. and Seppala, J., Observations on the Rate Enhancement
Effect with MgCl.sub.2 /TiCl.sub.4 and Cp.sub.2 ZrCl.sub.2 Catalyst
systems upon 1-Hexene Addition, 1993, Macromolecules 26 No. 21, pp
5535-5538. .
Corradini, P., et al., Hydrooligomerization of propene: a
"fingerprint" of a Ziegler-Natta catayst, 2, A reinterpretation of
results for isospecific homogeneous systems, 1992, Makromol. Chem.
, Rapid Commun. 13, pp 21-24. .
Busico, V., et al., Hydrooligomerization of propene: a
"fingerprint" of a Ziegler-Natta catayst, 1, Preliminary results
for MgCl.sub.2 supported systems, 1992, Makromol. Chem. , Rapid
Commun. 13, pp. 15-20. .
Ystenes, M., Predictions from the Trigger Mechanism for
Ziegler-Natta Polymerization of .alpha.-olefins, 1993, Makromol.
Chem. , Makromol. Symp. 66, pp. 71-82..
|
Primary Examiner: Wu; David W.
Assistant Examiner: Rabago; R.
Attorney, Agent or Firm: Innovation Law Group, Ltd. Dulin,
Esq.; Jacques M.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This Application is a Divisional of U.S. Ser. No. 09/097,234, filed
Jun. 12, 1998 by the same inventors, now U.S. Pat. No. 6,160,064,
issued Dec. 12, 2000, which in turn is a Regular Application
arising from: Provisional Application Ser. No. 60/054,335 filed
Jun. 14, 1997, entitled "Propylene Polymerization With Chiral and
Achiral Unbridged 2-Aryl Indene Metallocenes" (011 PROV);
Provisional Application Ser. No. 60/050,393 filed Jun. 19, 1997
entitled "Catalysts and EEF Process For The Synthesis of
Elastomeric Olefin Polymers" (010 PROV); Provisional Application
Ser. No. 60/050,105 filed Jun. 20, 1997, entitled "Thermoplastic
Elastomeric .alpha.-Olefin Homo- and Co-Polymers, Methods and
Fluxional Metallocene Catalysts Therefor (009 PROV); and
Provisional Application Ser. No. 60/071,050 filed Jan. 9, 1998,
entitled "Catalyst and Process For The Synthesis of Olefin Block
Copolymers" (013 PROV) the disclosures of each of which is hereby
incorporated by reference and the benefit of the priority of each
of which is hereby claimed under 35 USC .sctn.119 and .sctn.120.
Claims
We claim:
1. An elastomeric amorphous-crystalline blocks copolymer of at
least one alpha olefin monomor with ethylene having less than 10
mole % ethylene units, said ethylene is incorporated randomly
between the olefin units in the polymer chain, and said
elastoineric polymer is characterized by a melting point, T.sub.M,
above about 80.degree. C.
2. An elastomeric copolymer as in claim 1 wherein said ethylene
content is less than about 5 mole %.
3. An elastomeric copolymer as in claim 1 wherein said ethylene
content is less than about 3 mole %.
4. An elastomeric copolymer as in claim 1 wherein said T.sub.m is
above about 100.degree. C.
5. An elastomeric copolymer as in claim 2 wherein said T.sub.m is
above about 100.degree. C.
6. An elastomeric copolymer as in claim 3 wherein said T.sub.m is
above about 100.degree. C.
7. An elastomeric copolymer as in claim 1 wherein said T.sub.m is
above about 120.degree. C.
8. An elastomeric copolymer as in claim 2 wherein said T.sub.m is
above about 120.degree. C.
9. An elastomeric copolymer as in claim 3 wherein said T.sub.m is
above about 120.degree. C.
Description
TECHNICAL FIELD
This invention relates generally to processes for production of
.alpha.-olefin polymers using unbridged fluxional metallocenes,
primarily substituted aryl indenyl metallocenes, and more
particularly to use of unbridged, fluxional, cyclopentadienyl or
indenyl metallocene catalysts and catalyst systems in methods of
production of high melting point olefin homo- and co-polymers,
particularly elastomeric crystalline and amorphous block homo- and
co-polymers of alpha olefins. More specifically, the invention is
directed to: (1) the discovery and catalytic process use of a
Polymerization Rate-Enhancement effect (PRE effect) in
polymerization processes which involve the addition of minor
amounts of ethylene to the polymerization system to produce
polymers having properties ranging from crystalline thermoplastics
to high melting point thermoplastic elastomers to amorphous gum
elastomers, and methods for increasing polymerization production
rates and polymer molecular weight; (2) the discovery and catalytic
process use of an Elastomeric Property-Enhancement effect (EPE
effect) in which small quantities of ethylene added to the
polymerization system activates selected metallocene catalyst
systems, which otherwise do not produce elastomeric polymers, to
produce elastomeric polymers; and (3) novel substituted aryl
indenyl metallocene catalysts.
BACKGROUND
Crystalline, amorphous, and elastic polypropylenes are known.
Crystalline polypropylenes are generally regarded as comprising of
predominantly isotactic or syndiotactic structures and amorphous
polypropylene is regarded as comprising predominantly of an atactic
structure. U.S. Pat. Nos. 3,112,300 and 3,112,301 both of Natta,
et. al. describe isotactic and prevailingly isotactic
polypropylene.
U.S. Pat. No. 3,175,199 to Natta et al. describes an elastomeric
polypropylene which can be fractioned out of a polymer mixture
containing prevailingly isotactic and atactic polypropylenes. When
separated from the polymer mixture, a fraction of this polymer
showed elastomeric properties which were attributed to a
stereoblock structure comprising alternating blocks of isotactic
and atactic stereosequences. U.S. Pat. No. 4,335,225 discloses a
fractionable elastomeric polypropylene with a broad molecular
weight distribution.
Elastomeric polypropylenes with narrow molecular weight
distributions are also known which are produced in the presence of
bridged metallocene catalysts. Polymers of this type were described
by Chien et. al. in (J. Am. Chem. Soc. 1991, 113, 8569-8570), but
their low melting point renders them unsuitable for certain
applications. In addition, the activities of these catalyst systems
are low.
U.S. Pat. No. 5,594,080 discloses an unbridged, fluxional
metallocene catalyst system useful for the production of
elastomeric polyolefins. These fluxional, unbridged catalysts can
interconvert between geometric states on the time scale of the
growth of a single polymer chain in order to produce isotactic,
atactic stereoblock polyalphaolefins with useful elastomeric
properties. Polyolefins produced with these fluxional catalysts
systems can have a range of properties, from amorphous gum
elastomers to useful thermoplastic elastomers to non-elastomeric
thermoplastics.
The commercial utility of a catalyst system is closely tied to the
polymerization activity. Processes that lead to an increase in
activity of a polymerization system are of considerable practical
utility. The activity of a polymerization system can in some cases
be influenced by additives to the polymerization system. For
example for both classical Ziegler-Natta systems as well as
metallocene systems, the addition of hydrogen can result in an
increase in propylene polymerization activity, see Pasquet, V., et
al., Makromol. Chem. 1993, 194, 451-461 and references cited
therein. One of the explanations for the hydrogen effect is the
reactivation of the dormant sites resulting from 2,1-propylene
misinsertions, see Corradini, P., et al., Makromol. Chem., Rapid
Commun. 1992, 13, 15-20; Corradini, P., et al., Makromol. Chem.,
Rapid Commun. 1992, 13, 21-24; and Busico, V., et al., Makromol.
Chem., Rapid Commun. 1993, 14, 97-103. Since hydrogen is also a
chain transfer agent, the addition of hydrogen decreases the
molecular weight, which limits the practical utility of the
hydrogen effect where high molecular weight polymers are
desired.
Activation of ethylene polymerization systems by the addition of
small amounts of an alpha olefin is also known, see for example
Brintzinger, H., et. al. Angew. Chemie, Int. Ed. Engl. 1995, 34,
1143-1170. This so-called "comonomer effect" (see Spitz, R., et al.
Makromol. Chem. 1988, 189, 1043-1050) is useful in a process for
the synthesis of ethylene polymers, but not for alpha olefin
polymers. Hefert, N., et. al. Makromol. Chem. 1993 194, 3167-3182
report no effect of hexene on the rate of propene polymerization
with a metallocene catalyst. Several explanations have been
forwarded to explain this "comonomer effect" including a "trigger
mechanism" (Ystenes, M., Makromol. Chem. "Macromolecular Symposia"
1993, 66, 71-81) and improved rates of diffusion due to the
solubilization of active centers by incorporation of comonomer (see
Koivumaki, J., et al. Macromolecules 1993, 26, 5535-5538).
Activation of propylene polymerization systems in the presence of
5% ethylene have been previously reported for magnesium chloride
supported Ti-based catalysts by Spitz, R., et al. in Makromol.
Chem. 1988, 189, 1043-1050 and in Spitz, R., et al. in "Transition
Metal Catalyzed Polymerization", Quirk, R. P., Ed., Cambridge Univ.
Press 1988, pp. 719-728, and with V-based Ziegler catalysts by
Valvassori, A., et al. in Makromol. Chem. 1963, 61, 46-62. While
such "synergistic effects" have been observed with classical
Ziegler-Natta catalyst systems, Koivurnaki et. al. point out that
such synergistic effects do not work for homogeneous metallocene
systems (see Koivumaki, J., et al. Macromolecules 1993, 26,
5535-5538).
Accordingly, there is a need for processes to improve the activity
of metallocene catalysts systems capable of producing elastomeric
polypropylenes of high molecular weight with high melting
points.
THE INVENTION
SUMMARY, OBJECTS AND ADVANTAGES
We have discovered that the activity of fluxional unbridged
metallocene polymerization catalysts containing at least one
2-arylindene ligand may be increased by the addition of small
(typically 0.1-10 wt. %) amounts of ethylene to the polymerization
system. In particular, the addition of ethylene to a propylene
polymerization system derived from unbridged metallocene catalysts
containing at least one 2-arylindene ligand results in a
significant increase (up to ten-fold or above) in catalyst
activity. We term this increase in activity the Polymerization Rate
Enhancement effect (PRE), which can be measured in terms of an
Ethylene Enhancement Factor (EEF) as a dimensionless ratio. Also,
the molecular weight of the produced polymers may increase in the
presence of ethylene. The amount of ethylene included in the
reaction system can be selected and controlled to be so small as to
result in essentially minimal (<2 mole %) incorporation of
ethylene units into the polymer, yet surprisingly results in a
significant, disproportionately large increase in polymerization
activity. More specifically, by addition of small amounts of
ethylene into polypropylene reaction systems, an unexpectedly large
(order of magnitude or more) increase in activity is achieved to
produce elastomeric products.
Thus, in a first aspect of this invention, elastomeric olefin
polymers are formed using unbridged fluxional, metallocene-based,
catalyst systems in a polymerization process in which an
activity-enhancing amount of ethylene is incorporated into the
polymerization feed. This effect is herein termed the PRE effect,
for Polymerization Rate-Enhancement effect, and is quantified as a
dimensionless number in the range of from about 1.1 to about 10 or
above, called the EEF for Ethylene Enhancement Factor. Typically,
useful PRE (activity-enhancing) amounts of ethylene are above about
0.1 wt. % in the feed. Amounts of ethylene to generate the PRE
effect may be greater than 0.5 wt. % and preferably range up to
about 2 wt. %. However, if a polymer with more ethylene is desired,
additional gethylene may be incorporated into the polymerization
feed, including up to 10 to about 50 mole % based on olefin
units.
Even though ethylene may be introduced into a polymer of this
invention, only an activity-enhancing amount of ethylene for PRE is
required, i.e., to increase the activity of the fluxional,
metallocene-based, catalyst. Thus, a second important aspect of
this invention is the ability to use a PRE activity-enhancing
amount of ethylene in an olefin polymerization without
substantially affecting the physical properties of the elastomer.
Preferred elastomeric polymers containing ethylene linkages made
according to this invention have high melting temperatures (as
measured by DSC) above 80.degree. C., preferably about 100.degree.
C., including in the range of from about 120.degree. C. to about
140.degree. C. or above.
In a third important aspect of this invention, we have discovered
the ability to produce olefin (preferably propylene) elastomers
through incorporation of ethylene using unbridged fluxional
catalyst systems which may not otherwise produce acceptable
elastomeric homopolymers. This effect is herein termed the EPE
effect, for Elastomeric Property-Enhancing effect. The Elastomeric
Property-Enhancing amount of ethylene required to produce such
elastomers typically overlaps the aforesaid PRE activity-enhancing
amount. Incorporation of up to about 5 mole % or more of ethylene
typically will produce an elastomeric polymer using such catalyst
systems. Typical useful amounts of incorporated ethylene include
about 1 to 3 mole %. Again, a preferred polymer of this invention
retains sufficient crystallinity to provide a high melting point
(by DSC) of above 80.degree. C., preferably above 100.degree. C.,
including in the range of from about 120.degree. C. to about
140.degree. C. and above. For example, the novel Catalyst D of this
invention bis [2-(3,5-trifluoromethylphenyl)indenyl] zirconium
dichloride produces an elastomeric polypropylene with 9% ethylene
incorporated in the polymer with a T.sub.m of 100.degree. C. Even
with ethylene contents of up to about 10 mole % or more, polymers
of this invention typically show melting temperatures of 80.degree.
C. and above in contrast to conventional propylene-ethylene
copolymer elastomers produced by conventional catalysts which have
a lower melting temperature.
Polymers of this invention show a broad melting range by DSC
analysis and exhibit good elastic recoveries. The conventional
measurement of the melting point (T.sub.m) is the peak (or inverse
peak) in the DSC curve. Polymers of this invention also typically
retain properties after thermocycling of up to 100.degree. C. and
above. By way of example, such polymers retain transparency after
such a heat treatment and do not become opaque.
A preferred elastomeric I-olefin polymer of this invention is a
propylene polymer in which an amount of ethylene is incorporated
during polymerization such that the resulting elastomeric propylene
polymer maintains sufficient physical properties at elevated
temperature (such as melting temperature) to permit steam
sterilization without deformation of a shaped article fabricated
from the polymer. Typical steam sterilization conditions are
maintenance of a temperature of 121.degree. C. or above at a 2
atmosphere steam pressure.
Further, in polymerization systems which produce thermoplastic
crystalline propylene polymers, introduction of ethylene merely
reduces the melting point. In contrast, the EPE effect of this
invention unexpectedly results in converting the polymers to true
elastomers while providing a method of control over melting point
and retention of properties after thermocycling by adjustment of
the ethylene content in the feed and end product polymers.
As noted above, the class of metallocenes of this invention is
defined as "fluxional", meaning that the geometry of such
metallocene can change between two isomeric states. This change in
configuration occurs on a time scale that is slower than the rate
of olefin insertion, but faster than the average time to construct
(polymerize) a single polymer chain. The fluxional catalyst
structure is such that upon isomerization the catalyst symmetry
alternates between states that have different coordination
geometries and thus different steroselectivities. The catalyst
remains in that geometric symmetry for a time sufficient to be
characterizable as a "state", before rotating or otherwise
transforming to the other geometry or state. This geometric or
state alternation can be controlled by selecting ligand type and
structure to control rotation of the ligands on the ligand-metal
bond. Further, through control of polymerization, precise control
of the physical properties of the resulting polymers can be
achieved.
This invention includes novel processes for tailoring block size
distribution and resulting properties of the polymer such as:
tacticity, molecular weight, molecular weight distribution,
productivity, melt flow rate, melting point, crystallite aspect
ratio, tensile set and tensile strength by varying the structure of
the catalyst, the conditions of the polymerization reaction, and
the solvents, reactants, additives and adjuvants employed, the
latter adjuvants including use of ethylene in the PRE and EPE
effect processes described above and in the examples.
The catalyst system of the present invention consists of the
transition metal component metallocene in the presence of an
appropriate cocatalyst. In broad aspect, the transition metal
compounds have the formula: ##STR1##
in which M is a Group 3, 4 or 5 Transition metal, a Lanthanide or
an Actinide, X and X' are the same or different uninegative
ligands, such as but not limited to hydride, halogen, hydrocarbyl,
halohydrocarbyl, amine, amide, or borohydride substituents
(preferably halogen, alkoxide, or C.sub.1 to C.sub.7 hydrocarbyl),
and L and L' are the same or different substituted cyclopentadienyl
or indenyl ligands, in combination with an appropriate cocatalyst.
Exemplary preferred Transition Metals include Titanium, Hafnium,
Vanadium, and, most preferably, Zirconium. An exemplary Group 3
metal is Yttrium, a Lanthanide is Samarium, and an Actinide is
Thorium.
The ligands L and L' may be any mononuclear or polynuclear
hydrocarbyl or silahydrocarbyl, typically a substituted
cyclopentadienyl ring. Preferably L and L' have the formula:
##STR2##
where R.sub.1, R.sub.2 and R.sub.3 may be the same or different
substituted or unsubstituted alkyl, alkylsilyl or aryl substituents
of 1 to about 30 carbon atoms, and R.sub.9 and R.sub.10 may be the
same or different hydrogen, or substituted or unsubstituted alkyl,
alkylsilyl, or aryl substituents of 1 to about 30 carbon atoms.
Ligands of this general structure include cyclopentadiene, and
pentamethylcyclopentadiene. Other ligands L and L' of Formula 2 for
the production of propylene-ethylene copolymers include substituted
cyclopentadienes of the general formula: ##STR3##
where R.sub.4 -R.sub.10 have the same definition as R.sub.9 and
R.sub.10 above. Preferred cyclopentadienes of Formula 3 include
3,4-dimethyl-1-phenyl-1,3-cyclopentadiene (R.sub.2 =R.sub.3
=CH.sub.3, and R.sub.6 =H),
3,4-dimethyl-1-p-tolyl-1,3-cyclopentadiene (R.sub.2 =R.sub.3
=CH.sub.3, and R.sub.6 =CH.sub.3),
3,4,-dimethyl-1-(3,5-bis(trifluoromethyl)phenyl)-1,3-cyclopentadiene
(R.sub.2 =R.sub.3 =CH.sub.3, and R.sub.6 =CF.sub.3), and
3,4-dimethyl-1-(4-tert-butylphenyl)-1,3cyclopentadiene (R.sub.2
=R.sub.3 =CH.sub.3, and R.sub.6 =tBu).
Alternately preferred L and L' of Formula 1 include ligands wherein
R.sub.1 is an aryl group, such as a substituted phenyl, biphenyl,
or naphthyl group, and R.sub.2 and R.sub.3 are connected as part of
a ring of three or more carbon atoms. Especially preferred for L or
L' of Formula 1 for producing the homopolymers of this invention is
a 2-arylindene of formula: ##STR4##
Where R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9,
R.sub.10, R.sub.11, R.sub.12, R.sub.13, and R.sub.14 may be the
same or different hydrogen, halogen, aryl, hydrocarbyl,
silahydrocarbyl, or halohydrocarbyl substituents. That is, R.sub.1
of Formula 2 is R.sub.4 -R.sub.8 -substituted benzene, and R.sub.2,
R.sub.3 are cyclized in a 6-carbon ring to form the indene moiety.
Particularly preferred 2-aryl indenes include: 2-phenylindene;
1-methyl-2-phenyl indene; 2-(3,5-dimethylphenyl)indene;
2-(3,5-bis-triflouromethylphenyl)indene;
2-(3,5-bis-tertbutylphenyl)indene; 2-(3,5-bis
trimethylsilylphenyl)indene; 2-(4,-fluorophenyl)indene;
2-(2,3,4,5-tetrafluorophenyl)indene;
2-(2,3,4,5,6-pentaflourophenyl)indene; 2-(1-naphthyl)indene;
2-(2-naphthyl)indene; 2-[(4-phenyl)phenyl]indene; and
2-[(3-phenyl)phenyl]indene.
Preferred metallocenes according to the present invention include:
bis(2-phenylindenyl)zirconium dichloride;
bis(2-phenylindenyl)zirconium dimethyl;
bis(1-methyl-2-phenylindenyl)zirconium dichloride;
bis(1-methyl-2-phenylindenyl)zirconium dimethyl;
bis[2-(3,5-dimethylphenyl)indenyl]zirconium dichloride;
bis[2-(3,5-bis-trifluoromethylphenyl)indenyl]zirconium dichloride;
bis[2-(3,5-bis-tertbutylphenyl)indenyl]zirconium dichloride;
bis[2-(3,5-bis-trimethylsilylphenyl)indenyl]zirconium dichloride;
bis[2-(4,-fluorophenyl)indenyl]zirconium dichloride;
bis[2-(2,3,4,5,-tetraflorophenyl)indenyl]zirconium dichloride;
bis(2-(2,3,4,5,6-pentafluorophenyl)indenyl])zirconium dichloride;
bis[2-(1-naphthyl)indenyl]zirconium dichloride;
bis(2-(2-naphthyl)indenyl])zirconium dichloride;
bis(2-[(4-phenyl)phenyl]indenyl])zirconium dichloride;
bis[2-[(3-phenyl)phenyl]indenyl]zirconium dichloride;
(pentamethylcyclopentadienyl)(1-methyl-2-phenylindenyl)zirconium
dichloride; (pentamethylcyclopentadienyl)(2-phenylindenyl)zirconium
dichloride;
(pentamethylcyclopentadienyl)(1-methyl-2-phenylindenyl)zirconium
dirmethyl; (pentamethylcyclopentadienyl)(2-phenylindenyl)zirconium
dimethyl; (cyclopentadienyl)(1-methyl-2-phenylindenyl)zirconium
dichloride; (cyclopentadienyl)(2-phenylindenyl)zirconium
dichloride; (cyclopentadienyl)(1-methyl-2-phenylindenyl)zirconium
dimethyl; (cyclopentadienyl)(2-phenylindenyl)zirconium
dimethyl;
and the corresponding hafnium compounds such as:
bis(2-phenylindenyl)hafnium dichloride; bis(2-phenylindenyl)hafnium
dimethyl; bis(1-methyl-2-phenylindenyl)hafnium dichloride;
bis(1-methyl-2-phenylindenyl)hafnium dimethyl;
bis[2-(3,5-dimethylphenyl)indenyl]hafnium dichloride;
bis[2-(3,5-bis-trifluoromethyphenyl)indenyl]hafnium dichloride;
bis[2-(3,5-bis-tertbutylphenyl)indenyl]hafnium dichloride;
bis[2-(3,5-bis-trimethylsilylphenyl)indenyl]hafnium dichloride;
bis[2,(4-fluorophenyl)indenyl]hafnium dichloride;
bis[2-(2,3,4,5-tetrafluorophenyl)indenyl]hafnium dichloride;
bis[2-(2,3,4,5,6-pentafluorophenyl)indenyl]hafnium dichloride;
bis[2-(1-naphthyl)indenyl]hafnium dichloride;
bis[2-(2-naphthyl)indenyl]hafnium dichloride;
bis(2-((4-phenyl)phenyl)indenyl])hafnium dichloride;
bis[2-[(3-phenyl)phenyl]indenyl]hafnium dichloride;
(pentamethylcyclopentadienyl)(1-methyl-2-phenylindenyl)hafnium
dichloride; (pentamethylcyclopentadienyl)(2-phenylindenyl)hafnium
dichloride;
(pentamethylcyclopentadienyl)(1-methyl-2-phenylindenyl)hafnium
dimethyl; (pentamethylcyclopentadienyl)(2-phenylindenyl)hafnium
dimethyl; (cyclopentadienyl)(1-methyl-2-phenylindenyl)hafnium
dichloride; (cyclopentadienyl)(2-phenylindenyl)hafnium dichloride;
(cyclopentadienyl)(1-methyl-2-phenylindenyl)hafnium dimethyl;
(cyclopentadienyl)(2-phenylindenyl)hafnium dimethyl;
and the like.
Other metallocene catalyst components of the catalyst system
according to the present invention include:
bis(3,4-dimethyl-1-phenyl-cyclopentadienyl)zirconium dichloride;
bis(3,4-dimethyl-1-p-tolyl-cyclopentadienyl)zirconium dichloride;
bis(3,4-dimethyl-1-(3,5
bis(trifluoromethyl)phenyl)-cyclopentadienyl)zirconium dichloride;
bis(3,4-dimethyl-1-(4-tert-butylphenyl)-cyclopentadienyl)zirconium
dichloride;
and the corresponding hafnium compounds, such as:
bis(3,4-dimethyl-1-phenyl-cyclopentadienyl)hafnium dichloride;
bis(3,4-dimethyl-1-p-tolyl-cyclopentadienyl)hafnium dichloride;
bis(3,4-dimethyl-1-(3,5
bis(trifluoromethyl)phenyl)-cyclopentadienyl)hafnium dichloride;
bis(3,4-dimethyl-1-(4-tert-butylphenyl)-cyclopentadienyl)hafnium
dichloride;
and the like.
It should be understood that other unbridged, rotating, non-rigid,
fluxional metallocenes may be employed in the methods of this
intention, including those disclosed in our above-identified
Provisional applications, which are hereby incorporated by
reference to extent needed for support.
The Examples disclose a method for preparing the metallocenes in
high yield. Generally, the preparation of the metallocenes consists
of forming the indenyl ligand followed by metallation with the
metal tetrahalide to form the complex.
Appropriate cocatalysts include alkylaluminum compounds,
methylaluminoxane, or modified methylaluminoxanes of the type
described in the following references: U.S. Pat. No. 4,542,199 to
Kaminsky, et al.; Ewen, J. Am. Chem. Soc., 106 (1984), p. 6355;
Ewen, et al., J. Am. Chem. Soc. 109 (1987) p. 6544; Ewen, et al.,
J. Am. Chem. Soc. 110 (1988), p. 6255; Kaminsky, et al, Angew.
Chem., Int. Ed. Eng. 24 (1985), p. 507. Other cocatalysts which may
be used include Lewis or protic acids, such as B(C.sub.6
F.sub.5).sub.3 or [PhNMe.sub.2 H].sup.+ B(C.sub.6
F.sub.5).sup.-.sub.4, which generate cationic metallocenes with
compatible non-coordinating anions in the presence or absence of
alkyl-aluminum compounds. Catalyst systems employing a cationic
Group 4 metallocene and compatible non-coordinating anions are
described in European Patent Applications 277,003 and 277,004 filed
on Jan. 27, 1988 by Turner, et al.; European Patent Application
427,697-A2 filed on Oct. 09, 1990 by Ewen, et al.; Marks, et al.,
J. Am. Chem. Soc., 113 (1991), p. 3623; Chien, et al., J. Am. Chem.
Soc., 113 (1991), p. 8570; Bochmann et al., Angew. Chem. Intl. Ed.
Engl. 7 (1990), p. 780; and Teuben et al., Organometallics, 11
(1992), p. 362, and references therein.
The catalysts of the present invention consist of un-bridged,
non-rigid, fluxional metallocenes which can change their geometry
on a time scale that is between that of a single monomer insertion
and the average time of growth of a polymer chain. This is provided
by a non-rigid metallocene catalyst comprising cyclopentadienyl
and/or substituted cyclopentadienyl ligands substituted in such a
way that they can alternate in structure between states which have
different coordination geometries. This is achieved in the present
invention by using unbridged cyclopentadienyl ligands.
In one of many embodiments, these catalyst systems can be placed on
a suitable support such as silica, alumina, or other metal oxides,
MgCl.sub.2 or other supports. These catalysts can be used in the
solution phase, in slurry phase, in the gas phase, or in bulk
monomer. Both batch and continuous polymerizations can be carried
out. Appropriate solvents for solution polymerization include
liquified monomer, and aliphatic or aromatic solvents such as
toluene, benzene, hexane, heptane, diethyl ether, as well as
halogenated aliphatic or aromatic solvents such as CH.sub.2
Cl.sub.2, chlorobenzene, fluorobenzene, hexaflourobenzene or other
suitable solvents. Various agents can be added to control the
molecular weight, including hydrogen, silanes and metal alkyls such
as diethylzinc.
The metallocenes of the present invention, in the presence of
appropriate cocatalysts, are useful for the homo-polymerization
(and co-polymerization) of alpha-olefins, such as propylene,
1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and
combinations thereof, and of copolymerization with ethylene. The
polymerization of olefins is carried out by contacting the
olefin(s) with the catalyst systems comprising the transition metal
component and in the presence of an appropriate cocatalyst, such as
an aluminoxane, or a Lewis acid such as B(C.sub.6 F.sub.5).sub.3.
In co-monomer systems, and in particular ethylene-propylene monomer
systems, productivities in excess of 41 kg/g for the
copolymerizations has been attained [see Example 85]
The metallocene catalyst systems of the present invention are
particularly useful for the polymerization of propylene monomers
and propylene-ethylene monomer mixtures to produce polypropylenes
and propylene-ethylene co-polymers with novel elastomeric
properties. By elastomeric, we mean a material which tends to
regain its shape upon extension, such as one which exhibits a
positive power of recovery at 100%, 200% and 300% elongation. The
properties of elastomers are characterized by several variables.
The tensile set (TS) is the elongation remaining in a polymer
sample after it is stretched to an arbitary elongation (e.g. 100%
or 300%) and allowed to recover. Lower set indicates higher
elongational recovery. Stress relaxation is measured as the
decrease in stress (or force) during a time period (e.g. 30 sec. or
5 min.) that the specimen is held at extension. There are various
methods for reporting hysteresis during repeated extensions. In the
present application, retained force is measured as the ratio of
stress at 50% elongation during the second cycle recovery to the
initial stress at 100% elongation during the same cycle. Higher
values of retained force and lower values of stress relaxation
indicate stronger recovery force. Better general elastomeric
recovery properties are indicated by low set, high retained force
and low stress relaxation.
It is believed that the elastomeric properties of the
polypropylenes and propylene-ethylene copolymers of this invention
are due to an alternating block structure comprising of isotactic
and atactic stereo-sequences. Without being bound by theory, it is
believed that isotactic block stereosequences tightly interlocked
with one another provide crystalline blocks which can act as
physical crosslinks in the polymer network. These crystalline
blocks are separated from one another by intermediate, atactic
lengths of the polymer which enable the polymer to elastically
deform. While we do not wish to be bound by theory it is believed
the ethylene is incorporated randomly between the propylene units
in the chain.
The structure of the polymers may be described in terms of the
isotactic pentad content [mmmm] which is the percentage of
isotactic stereosequences of 5 contiguous stereocenters, as
determined by .sup.13 C NMR spectroscopy (Zambelli, A., et al.
"Model Compounds and .sup.13 C NMR Observation of Stereosequences
of Polypropylene" Macromolecules 1975, 8, 687-689). The isotactic
pentad content of statistically atactic polypropylene is
approximately 6.25%, while that of highly isotactic poly-propylene
can approach 100%. For co-polymers the isotactic pentad content may
be defined as the ratio of the area of PmPmPmPmPm+PmPmPmPmPE peaks
over the area of all methyl peaks.
While it is possible to produce propylene homopolymers and
copolymers with ethylene having a range of isotactic pentad
contents, the elastomeric properties of the polymer will depend on
the distribution of isotactic (crystalline) and atactic (amorphous)
stereosequences, as well as the distribution of comonomer in the
copolymer. Semicrystalline thermoplastic elastomers of the present
class of materials consist of amorphous-crystalline block polymers,
and thus the blockiness of the polymer determines whether it will
be elastomeric. Crystallizable isotactic block length and content
must be sufficient to provide a crosslinked network with usefully
high Tm, but below the crystallinity of a hard plastic.
We have discovered that the structure, and therefore the properties
of the alpha olefin polymers obtained with the catalysts of the
present invention are dependent on olefin concentration, the ratio
of olefins in the feed, the nature of the ligands, reactant
pressure, the temperature of the polymerization, the nature of the
transition metal, the ligands on the metallocene, the nature of the
cocatalyst, and the reaction system.
It will be appreciated from the illustrative examples that the
catalyst systems of this invention provide a broad range of polymer
properties from the polymerization process of this invention.
Polymers which range in properties from non-elastomeric
thermoplastics to thermoplastic elastomers can be readily obtained
by suitable manipulation of the metallocene catalyst, the reaction
conditions, or the cocatalyst to give all by proper choice of
process conditions and catalyst.
Without being bound by theory, it is believed that it is critical
for the present invention to have a catalyst which can isomerize
between states on a time scale that is slower than the rate of
olefin insertion but faster than the average time to construct a
single polymer chain in order to obtain a block structure. In
addition, to produce elastomeric polymers, the catalyst complex
isomerizes between states which have different coordination
geometries. This is provided in the present invention by
metallocene catalysts comprising of unbridged
cyclopentadienyl-based ligands which are substituted in such a way
that they can exist in different geometric states during the course
of the polymerization reaction.
Based on the evidence to date, it appears that the rotation of the
cyclopentadienyl ligands provides a mechanism for the alternation
of catalyst geometry between the two states. The average block size
distribution for a polymer produced with a catalyst which can
change its state is controlled by the relative rate of
polymerization versus catalyst isomerization as well as the
steady-state equilibrium constant for the various coordination
geometries (e.g. chiral vs. achiral). The catalysts of this
invention provide a means of producing polypropylenes and other
alpha olefins with a wide range of isotactic and atactic block
lengths by changing the substituents on the cyclopentadienyl
ligands of the metallocene. It is believed that modification of the
cyclopentadienyl ligands and/or the nature of the transition metal
will alter one or more of the following: The rate of
polymerization, the rate of catalyst isomerization, and the
steady-state equilibrium constant between the various coordination
geometries, all of which will affect the block lengths and block
length distribution in the resulting polymer. For example, it is
believed that introduction of larger substituents on the
cyclopentadienyl ligands will slow the rate of rotation and thereby
increase the block lengths in the polymer. Of particular interest
is the ability to produce high melting thermoplastic elastomers
from catalysts which normally produce only non-elastomeric
thermoplastics by the incorporation of small amounts of a second
olefin. The comonomer is believed to insert randomly into the
isotactic and atactic blocks, thereby disrupting crystallinity, but
still providing a thermoplastic elastomer network (i.e. alternating
stereoblock structure) with sufficient isotactic block lengths to
achieve high melting polymers.
As described in U.S. Pat. No. 5,594,080, the disclosure of which is
incorporated by reference herein, fluxional catalysts of the type
described herein are useful for the production of elastomeric
polyolefins. The productivity of catalyst systems has a large
influence on their commercial viability; we have found that
addition of small amounts of ethylene to a reaction system useful
for the preparation of polyolefin elastomers has a quite unexpected
and beneficial effect of increasing the productivity of the
reaction system dramatically. It is known that most polymerization
catalysts are more active for ethylene polymerization than alpha
olefin polymerization, thus a somewhat higher productivity might be
expected for a polymerization system containing both ethylene and
an alpha olefin. However, the disproportionately large and
unexpected increase in productivity of the catalysts systems of the
present invention in the presence of as little as 0.6 weight
percent ethylene in the reaction system is not predictable from
prior works, and is evidence for the non-linear increase in
productivity which we term the "Polymerization Rate-Enhancement
effect" (PRE effect), which is quantifiable in terms of an
"Ethylene Enhancement Factor" or EEF. The ethylene enhancement
factor EEF can be calculated from the well-known equations which
describe the copolymerization of olefins. By way of illustration,
we derive these equations for the effect of ethylene on propylene
polymerization, but the Polymerization Rate-Enhancement effect will
apply in the case of other alpha olefins as well.
The rate of olefin polymerization in the presence of hvo monomers
such as ethylene and propylene can be described by 1st order Markov
model given by the following four equations: ##STR5##
where M.sub.e and M.sub.p are the active centers with the last
ethylene and propylene inserted units, respectively and k.sub.ee is
the rate constant for ethylene insertion at an ethylene site
M.sub.e, and k.sub.ep is the rate constant of propylene insertion
at an ethylene site M.sub.e, etc . . . . The rate of polymerization
in the presence of both ethylene and propylene, R.sub.ep, can be
expressed as:
Since, under steady-state conditions, the rates of interconversion
of M.sub.e into M.sub.p and of M.sub.p into M.sub.e are equal:
and we can express [M.sub.e ] through [M.sub.p ] as:
At low ethylene concentrations in the feed, where [P]=[P.sup.h ],
the ratio of the rate of polymerization in the presence of both
monomers, R.sub.ep, to the rate of propylene polymerization,
R.sub.pp, is: ##EQU1##
where k.sub.pp.sup.h, M.sub.p.sup.h, P.sup.h signify the values for
propylene polymerization in the absence of ethylene, and k.sub.ee
/k.sub.ep =r.sub.e and k.sub.pp /k.sub.pe =r.sub.p.
The ratio of the rates of polymerization in the presence and
absence of ethylene are related to the ratio of the corresponding
productivities, P.sub.ep and P.sub.pp : ##EQU2##
In equation 5 the increase of polymerization productivity due to
the faster rate of ethylene insertion is described by expression
(r.sub.e [E].sup.2 /r.sub.p[P].sup.2 +2[E]/(rp[P])+1). The
expression k.sub.pp [M.sub.p ]/k.sub.pp.sup.h [M.sub.p.sup.h ] is
the Ethylene Enhancement Factor (EEF) and describes the ratio of
the rate of consecutive propylene-propylene insertions in the
presence of ethylene as compared to the rate in the absence of
ethylene: ##EQU3##
If there is no ethylene enhancement effect, then the EEF should be
equal to unity, that is EEF=k.sub.pp [M.sub.p ]/(k.sub.pp.sup.h
[M.sub.p.sup.h ])=1. An EEF greater than one is a metric that
signifies an unexpected and non-linear increase in productivity in
the presence of ethylene that cannot be anticipated due to the
greater rate of ethylene insertion relative to that of alpha
olefins.
For the catalysts of the present invention, we find dramatic and
non-linear increases in productivities of alpha olefins in the
presence of minor amounts of ethylene. Catalyst systems containing
as little as 0.6% by weight of ethylene in the feed result in more
than a two-fold increase in productivity (EEF=2.2) to give
elastomeric polyolefins. In another example, as little as 5 wt. %
ethylene in the feed results a 10-fold increase in productivity to
give useful elastomeric products. Thus, one of the benefits of the
Polymerization Rate-Enhancement effect (PRE effect) of this
invention is that catalyst systems which in the absence of ethylene
might be of marginal or little commercial interest are useful for
the production of elastomeric polymers.
By using the novel metallocene catalyst systems of the invention
without ethylene, we obtain polymers which range in properties from
non-elastomeric thermoplastics to useful elastomeric .alpha.-olefin
polymers. By use of ethylene as described herein to take advantage
of the Polymerization Rate-Enhancement effect, elastomeric
.alpha.-olefin polymers may be obtained, but at rates up to ten
fold greater than the use of the same catalyst systems without the
ethylene.
Furthermore, by use of the novel metallocene catalysts of the
present invention we obtain alpha olefin (preferably propylene)
elastomers by adding ethylene to an unbridged fluxional metallocene
polymerization system which may not otherwise produce useful
elastomeric homopolymers. By use of certain metallocene catalysts
of the present invention, a remarkable improvement in the
properties of propylene homopolymers can be realized by
incorporation of small amounts of ethylene (10% or less). For
example, polymerization of propylene with certain catalysts of the
present invention can yield non-elastomeric propylene homopolymers
with tensile sets above 39%, stress relaxation above 60% and no
retained force. Incorporation of small amounts (10% or less) of
ethylene into these polymerization system surprisingly results in
polymers with good elastomeric properties. This is an example of
the Elastomeric Property-Enhancement (EPE) effect.
The polymers of the present invention have useful elastomeric
properties. These are a consequence the degree of crystallinity in
the polymers which is controlled by the use of the catalysts and
ethylene enhancement processes of this invention. The degree of
crystallinity of the polymers of this invention are typically in
the range of 1-40%, preferably in the range of 5-30% and most
preferably in the range of 10-25%. The melting points of the
polymers of the present invention are typically above 80.degree.
C., preferably above 100.degree. C., including those in the range
of 120.degree. C. to 140.degree. C. and above. The elastomeric
polymers of the present invention exhibit tensile moduli in the
range of 2-30 MPa, with values preferably below 20 MPa and most
preferably below 15 MPa. The elastomeric polymers of the invention
exhibit a positive force of recovery upon elongation. Typically,
the retained force at 50% extension following 100% elongation is in
the range of 10-50%, preferably in the range of 15-50%, and most
preferably in the range 20-50%. The recovery properties of the
polymers are also very good as evidenced by tensile set at 100%
elongations of typically less than 50%, preferably less than 20%
and most preferably less than 10%.
DETAILED DESCRIPTION OF CARRYING OUT THE INVENTION
The following detailed description illustrates the invention by way
of example, not by way of limitation of the principles of the
invention. This description will clearly enable one skilled in the
art to make and use the invention, and describes several
embodiments, adaptations, variations, alternatives and uses of the
invention, including what is presently believed to be the best mode
of carrying out the invention.
I. METALLOCENE CATALYST PREPARATION
EXAMPLE 1
Preparation of 2-Phenylindene, (Ligand 1)
A solution of 2-indanone (13.47 g, 102 mmol) in anhydrous benzene
(100 mL) was added to phenylmagnesium bromide (3.0 M in diethyl
ether, 50.9 mL, 153 mmol) at 5.degree. C. over 2.5 hours. The
reaction was allowed to warm to room temperature over 30 minutes.
The solution was cooled to 0.degree. C. and 150 mL of water are
added. The resultant mixture was diluted with 200 mL of hexanes,
neutralized with 5 M HCl, and washed with brine (2.times.100 mL).
The aqueous layer was extracted with hexanes (2.times.50 mL), and
the combined organic layers were dried (MgSO.sub.4), filtered, and
the solvent removed in vacuo from the filtrate to yield a brown
oil. This oil and p-toluenesulfonic acid (0.50 g) were dissolved in
benzene (250 mL) in a round-bottom flask below a Soxhlet extractor
containing 4.ANG. molecular sieves. After refluxing for 2.5 hours,
the solution was filtered and cooled to 5.degree. C. overnight. The
product, a white flaky solid, was collected by filtration, and was
washed with 50 mL of cold benzene. Additional product is obtained
by concentrating the filtrate, cooling, and filtering the crystals
(12.60 g, 64.3% yield). .sup.1 H NMR (400 MHz, 20 C, CDCl.sub.3)
7.62 (d, J=7.3 Hz, 2H), 7.47 (d, J=7.3 Hz, 1H), 7.39 (M, 3H), 7.27
(m, 2H), 7.22 (s, 1H), 7.18 (t, J=7.4 Hz, 1H), 3.78 (S<2H).
.sup.13 C{.sup.1 H} NMR (100 MHz, 20 C, CDCl.sub.3): 146.3, 145.3,
143.1, 135.9, 128.6, 127.5, 126.5, 126.4, 125.6, 124.7, 123.6,
120.9, 38.9.
EXAMPLE 2
Preparation of Bis(2-Phenylindenyl)zirconium Dichloride, Catalyst A
(Ligand 1)
A solution of n-butyllithium (1.6 M in hexanes, 3.25 mL, 5.2 mmol)
was added to a solution of 2-phenylindene (1.01 g, 5.3 mmol) in
tetrahydrofuran (40 mL) at -78.degree. C. over 2 minutes. The
orange solution was warmed to room temperature over 30 minutes.
After solvent is removed in vacuo, the yellow solid was suspended
in toluene (25 mL). To this mixture was added a suspension of
ZrCl.sub.4 (612 mg, 2.6 mmol) in toluene (25 mL) at room
temperature. This yellow solution was stirred for 2.5 h, heated to
80 C, and filtered over a medium frit packed with Celite. The
Solution was cooled to -20 C overnight, resulting in the formation
of yellow-orange rod-like crystals of bis (2-phenylindenyl)
zirconium dichloride (1.173 g, 82.0% yield). .sup.1 H NMR (400 MHz,
20 C, C.sub.6 D.sub.6): .LAMBDA. 7.38 (d, J=7.1 Hz, 4H), 7.17 (m,
4H), 7.10 (m, 2H), 7.04 (dd, J=6.5, 3.1 Hz, 4H), 6.90 (dd, J=6.5,
3.1 Hz, 4H), 6.41 (s, 4H). .sup.13 C{.sup.1 H} NMR (100 MHz, 20 C,
C.sub.6 D.sub.6) .LAMBDA. 133.6, 132.7, 128.9, 128.5, 127.2, 126.9,
126.7, 125.1, 103.6.
EXAMPLE 3
Preparation of Bis(2-Phenylindenyl)zirconium Dimethyl, Catalyst B
(Ligand 1)
A solution of methyllithium (1.4 in diethyl ether, 0.75 mL, 1.05
mmol) was added to a solution of bis(2-phenyl-indenyl)zirconium
dichloride (280 mg, 0.51 mmol) in diethyl ether (100 mL) at
-100.degree. C. The bright yellow solution is warmed to room
temperature over 30 minutes. After 3 hours, volatiles were removed
from the colorless solution and toluene was added (25 mL). The
solution was filtered over a medium frit packed with Celite, and
solvent is removed in vacuo. Crystallization from toluene (1 mL)
and pentane (15 mL) yields cream colored cubes (110 mg, 42.5%).
.sup.1 H (400 MHz, 20 C, C.sub.6 D.sub.6): .LAMBDA. 7.28 (m, 4H),
7.16 (m, 6H), 702 (dd, J=6.4, 3.2 Hz, 4H), 6.93 (dd, J=6.5, 3.2 Hz,
4H), 6.00 (s, 4H), -0.85 (s, 6H).
EXAMPLE 4
Preparation of Bis(2-Phenylindenyl)hafnium Dichloride, Catalyst C
(Ligand 1)
A solution of n-butyllithium (2.5 M in hexanes, 2.45 mL, 61 mmol)
was added to a solution of 2-phenylindene (1.18 g, 61 mmol) in
tetrahydrofuran (40 mL) at -78.degree. C. over 2 minutes. The
orange solution was warmed to room temperature over 30 minutes.
After solvent was removed in vacuo, the orange oil was suspended in
toluene (65 mL). To this mixture was added a suspension of
HfCl.sub.4, (99.99% Hf, 980 mg, 3.1 mmol) in toluene (5 mL) at room
temperature. This rust colored solution was stirred in the dark for
3 hours and filtered over a medium frit packed with Celite. Solvent
is removed to yield a dark orange solid. A 100 mg sample was freed
from unreacted ligand by sublimation at 120 C. Recrystallization
from toluene at -20.degree. C. overnight yields a dark yellow solid
(28 mg, 28% yield). .sup.1 H NMR (400 MHz 20.degree. C. C.sub.6
D.sub.6): .LAMBDA. 7.36 (d, J=7.2 Hz, 4H), 7.18 (m, 4H), 7.12 (m,
2H), 7.07 (dd, J=6.6, 3.1 Hz, 4H) 6.88 (dd, J=6.6, 3.1 Hz, 4H),
6.29 (s, 4H). .sup.13 C {.sup.1 H) NMR (100 MHz) 20.degree. C.,
C.sub.6 D.sub.6): .LAMBDA. 132.7, 132.1, 128.8, 128.5, 127.2,
126.1, 125.1, 101.4.
EXAMPLE 5
Preparation of 2-(Bis-3,5-Trifluoromethylphenyl)indene, Ligand
2
A 3-neck 500 mL round-bottomed flask fitted with a condenser and an
addition funnel was charged with 2.62 g (0.11 mol) of Mg turnings
and 20 mL of anhydrous diethyl ether. Slow addition of a solution
of 25.10 g (0.09 mol) of 3,5-bis(trifluoromethyl) bromobenzene in
diethyl ether (100 mL), followed by refluxing for 30 min, gave a
brown-grey solution of the aryl Grignard reagent. The solution was
cooled to room temperature, filtered over a plug of Celite and
evacuated to yield a brown oil. Toluene (40 mL) was added and the
suspension cooled to 0.degree. C. whereupon a solution of
2-indanone (9.22 g, 0.07 mol) in toluene (60 mL) was added dropwise
to give a tan-brown slurry. This mixture was warmed to room
temperature and stirred for an additional 3 hours. After cooling to
a 0.degree. C. it was quenched with 150 mL of water. Hexane (200
mL) was added and the reaction mixture neutralized with 5M HCl. The
organic layer was separated, and the aqueous layer was extracted
with two 50-mL portions of hexane. The combined organic layers were
washed with two 50-mL portions of brine and dried over anhydrous
magnesium sulfate. After filtration over Celite, the solvent was
removed under vacuo yielding 21.5 g (89% based on 2-indanone) of
2-(bis-3,5-(trifluoromethyl)phenyl)indanol as an off-white solid.
.sup.1 H NMR (DCDl.sub.3, 23 C, 400 MHz): .LAMBDA. 8.05 (s, 2H),
7.80 (s, 1H), 7.5-7.0 (M, 4H), 3.41 (m, 4H), 2.21 (s, 1H, OH).
Under argon, this alcohol (21.5 g, 0.06 mol) and p-toluene-sulfonic
acid monohydrate (800 mg) were dissolved in toluene (250 mL) and
the solution was heated to reflux for 6 hours to afford 14.4 g,
(70%) of 2-(bis-3,5(trifluoromethyl)-phenyl)indene upon
recrystallization from diethyl ether/hexane at -18 C. .sup.1 H NMR
(CDCl.sub.3, 23.degree. C., 400 MHz): .LAMBDA. 8.01 (s, 2H,
Ar.sub.f), 7.75 (s, 1H, A.sub.rf), 7.52 (d, J=7 Hz, 1H), 7.47 (d,
J=7 Hz, 1H), 7.43 (s, 1H), 7.33 (dd, 2J=7 Hz, 1H), 7.27 (dd, 2J=7
Hz, 1H), 2.83 (s, 2H). .sup.13 C NMR (CDCl3, 23 C, 100 MHz):
.LAMBDA. 144.3 (s), 143.1 (s), 138.0 (s), 132.1 (q, .sup.2
J.sub.C-F =33 Hz), 130.1 (d, J.sub.C-H =167 Hz), 127.0 (dd),
J.sub.C-H =160 Hz, .sup.2 J.sub.C-H =7 Hz), 126.0 (dd, J.sub.C-H
=159 Hz, .sup.2 J.sub.C-H =7 Hz)m 125.2 (brd, J.sub.C-H =162 Hz),
123.9 (dd, J.sub.C-H =156 Hz, .sup.2 J.sub.C-H =9 Hz), 123.4 (q,
J.sub.C-F =273 Hz, CF.sub.3), 121.8 (dd, J.sub.C-H =160 Hz, .sup.2
J.sub.C-H =8 Hz), 120.6 (brd, J.sub.C-H =167 Hz), 38.9 (td,
J.sub.C-H =127 Hz, .sup.2 J.sub.C-H =7 Hz, CH.sub.2). C,H analysis:
Anal. Found (Calcd): C, 62.45 (62-20); H 3.01 (3.07).
EXAMPLE 6
Preparation of
Bis(2-(Bis-3,5-Trifluoromethyl)phenyl)indenyl)zirconium Dichloride,
Catalyst D (Ligand 2)
N-Butyllithium (2.5 M in hexanes, 850 mL, 2.13 mmol) was added to a
solution of 2-(bis-3,5(trifluoromethyl)phenyl)indene (648 mg, 1.97
mmol) in toluene (15 mL). The heterogeneous solution was stirred at
ambient temperature for 4 hours 30 minutes to give a green-yellow
solution which was treated with a suspension of ZrCl.sub.4 (240 mg,
1.03 mmol)in toluene (20 mL) via cannula. The yellow suspension was
stirred at ambient temperature for 2 hours 30 minutes, heated to
ca. 80 C, and filtered over a plug of Celite. After washing the
Celite with hot toluene several times (3.times.10 mL), the filtrate
was concentrated and cooled to 18 C to give 442 mg (55%) of light
yellow crystals of
Bis(2-(Bis-3,5-trifluoromethylphenyl)-indenyl)zirconium dichloride,
catalyst D. .sup.1 H NMR (C.sub.6 D.sub.6, 23 C, 400 MHz): .LAMBDA.
7.67 (s, 2H, arf), 7.55 (s, 4H, Arf), 7.19 (m, 4H, Ar), 6.89 (m,
4H, Ar), 5.96 (s, 4H, Cp-H). 13C NMR (C.sub.6 D.sub.6, 23 C, 100
MHz: .LAMBDA. 135.6 (s), 133.1 (s), 131.6 (q, .sup.2 J.sub.C-F =33
Hz), 127.1 (brd, J.sub.C-H =161 Hz), 126.8 (s), 126.4 (dd,
J.sub.C-H =161 Hz, .sup.2 J.sub.C-H =8 Hz), 125.4 (dd, J.sub.C-H
=167 Hz), .sup.2 J.sub.C-H =5 Hz), 123.8 (q, J.sub.C-F =273 Hz,
C-.sub.F), 121.8 (brd, J.sub.C-H =159 Hz), 102.5 (dd, J.sub.C-H
=176 Hz, .sup.2 J.sub.C.sub.H =7 Hz), Cp (C-H). C,H analysis: Anal.
found (Calcd.): C, 49.99 (50.01); H 2.32 (2.22).
EXAMPLE 7
Preparation of
Bis(2-(Bis-3,5-Trifluoromethyl-phenyl)indenyl)hafnium Dichloride,
Catalyst E (Ligand 2)
N-Butyllithium (1.6M in hexanes, 2 mL, 3.20 mmol) was added
dropwise at ambient temperature to a solution of
2-(bis-3,5(trifluoromethyl)phenyl)indene (1.03 g, 3.14 mmol) in
diethyl ether (10 mL). After stirring for 30 min, the solvent was
removed in vacuo leaving a green-yelow solid. In a drybox,
HfCl.sub.4, (510 mg, 1.59 mmol) was added to the lithium salt. The
solids were then cooled to -78 C at which temperature toluene (45
mL) was slowly added. The flask was allowed to reach ambient
temperature and the suspension was stirred for 24 hours after which
time it was heated for 15 min to ca. 80 C (heat gun). The solvent
was then removed in vacuo. The solid was extracted with CH.sub.2
Cl.sub.2 (50 mL) and the solution filtered over a plug of Celite.
After washing the Celite with 4.times.15 mL CH.sub.2 Cl.sub.2, the
solvent was removed under vacuo from the filtrate. The solid was
dissolved in 15 mL of CH.sub.2 Cl.sub.2, filtered and over filtrate
a layer of hexane (40 mL) was slowly added. Crystals of
Bis(2-(Bis-3,5-trifluoromethylphenyl)indenyl)hafnium dichloride
Catalyst E were obtained from this layered solution at -18 C.
.sup.1 H NMR (C.sub.6 D.sub.6, 23.degree. C., 200 MHz); .LAMBDA.
7.65 (s, 2H, Ar.sub.f), 7.51 (s, 4H, Ar.sub.f), 6.7-7.3 (m, 8H Ar),
5.63 (s, 4H, Cp-H). .sup.13 C NMR (C6D6 23.degree. C., 100 MHz):
.LAMBDA. 135.8 (s), 132.9 (s), 131.6 (q, .sup.2 J.sub.C-F =34 Hz),
127.2 (brd, J.sub.C-H =160 Hz), 126.3 (dd, J.sub.C-H =161 Hz,
.sup.2 J.sub.C-H =8 Hz), 126.0 (s), 125.6 (dd, J.sub.C-H =167 Hz,
.sup.2 J.sub.C-H =5 Hz), 123.8 (q, J.sub.C-F =273 Hz, CF.sub.3),
121.7 (brd, J.sub.C-H =161 Hz), 100.1 (dd, J.sub.C-H =176 Hz,
J.sub.C-H =6 Hz, Cp C-H). C, H analysis: Anal. Found (Calcd.): C,
45.10 (45-18); H, 1.87 (2.01).
EXAMPLE 8
Preparation of 2-(4-Tert-butylphenyl)indene, (Ligand 3)
3-neck 250 mL round-bottomed flask fitted with a condenser and an
addition funnel was charged with 1.48 g (0.06 mol) of Mg turnings
and 10 mL of anhydrous diethyl ether (70 mL), followed by refluxing
for 1 hour, gave a yellow solution of the aryl Grignard reagent.
The solution was cooled to room temperature, filtered over a plug
of Celite, and evacuated to yield a yellow foam. Toluene (15 mL)
was added and the suspension cooled to 0.degree. C. and treated
dropwise with a solution of 2-indanone (4.97 g, 0.04 mol) in
toluene (35 mL) to give an off-white slurry. The heterogeneous
reaction mixture was warmed to room temperature and stirred for an
additional 30 minutes. After cooling to 0.degree. C. it was
quenched with 74 mL of water. Hexane (75 mL) was added and the
reaction mixture was neutralized with 5M HCl. The organic layer was
separated, and the aqueous layer was extracted with two 15-mL
portions of hexane. The combined organic layers were washed with
two 30-mL portions of brine and dried over anhydrous magnesium
sulfate. After filtration over Celite, the solvent was removed
under vacuo yielding a yellow oily solid. The solid was triturated
with small portions of hexane to give 4.65 g (46% based on
2-indanone) of 2(4-t-butylphenyl)indanol as a white solid. .sup.1 H
NMR (CDCl.sub.3, 23.degree. C., 400 MHz): .LAMBDA. 7.6-7.0 (m, 8H),
3.40 (m, 4H), 2.16 (s, 1H, OH), 1.25 (s, 9H, tBu).
Under argon, this alcohol (4.3 g, 0.06 mol) and p-toluenesulfonic
acid monohydrate (120 mg) were dissolved in benzene (74 mL) and the
solution was heated to reflux for 2 hours 30 minutes to give
2-(4-t-butylphenyl)indene, which was recrystallized from diethyl
ether/hexane at -18.degree. C. (2.74 g, 68%). .sup.1 H NMR
(CDCl.sub.3, 23.degree. C., 400 MHz): .LAMBDA. 7.59 (d, J=8.5 Hz,
2H), 7.47 (d, J=7Hz, 1H), 7.42 (d, J=8.5 Hz, 2H), 7.40 (d, J=7 Hz,
1H), 7.28 (dd, 2J=7 Hz, 1H), 7.20 (s, 1H), 7.18 (dd, 2J=7 Hz, 1H),
3.79 (s, 2H) 1.36 (s, 9H, t-Bu). .sup.13 C NMR (CDCl.sub.3,
23.degree. C., 100 MHz): .LAMBDA. 150.7 (s), 146.4 (s), 145.6 (s),
143.1(s), 126.6 (dd, J.sub.C-H =159 Hz, .sup.2 J.sub.C-H =7 Hz),
125.8 (d, J.sub.C-H =163 Hz), 125.6 (dd, J.sub.C-H =157 Hz, .sup.2
J.sub.C-H =7 Hz), 125.4 (dd, J.sub.C-H =7 Hz), 124.5 (dd, J.sub.C-H
=159 Hz, .sup.2 J.sub.C-H =7 Hz), 123.6 (dd, J.sub.C-H =158 Hz,
.sup.2 JCH=8 Hz), 120.8 (dd, J.sub.C-H =159 Hz, 2JCH=8 Hz), 39.0
(td, J.sub.C-H =128 Hz), .sup.2 J.sub.C-H =6 Hz, CH.sub.2), 34.6
(s, C(CH.sub.3).sub.3), 31.3 (brq, J.sub.C-H =126 Hz,
C(CH.sub.3).sub.3). Anal. found (calcd.): C, 91.40 (91.88); H, 7.98
(8.12).
EXAMPLE 9
Preparation of Bis(2-(4-Tert-butylphenyl)indenyl)zirconium
Dichloride, Catalyst F (Ligand 3)
N-Butyllithium (1-6 M in hexanes, 1.84 mL, 2.88 mmol) was added to
a solution of 2-(4-t-butylphenyl)indene (710 mg, 2.86 mmol) in
tetrahydrofuran (15 mL) at -78.degree. C. The orange solution was
warmed to ambient temperature and stirred for 30 minutes. The
solvent was then removed in vacuo to give a yellow solid. The
Schlenk flask was cooled to -78.degree. C. and 15 mL of toluene
were added. Then, a suspension of ZrCl.sub.4 (333 mg, 1.43 mmol) in
toluene (15 mL) was added via cannula. The solution was warmed to
room temperature and stirred for 1.5 hours to give a black-red
solution, which was filtered over a plug of Celite. After washing
the Celite with toluene several times (3.times.10 mL), the filtrate
was concentrated and cooled to -18.degree. C. to give 267 mg (28%
of Bis(2-(4-tert-butylphenyl)indenyl)zirconium dichloride as orange
crystals. .sup.1 H NMR (C.sub.6 D.sub.6, 23.degree. C., 400
MHz):
.LAMBDA. AB pattern centered at 7.42 ppm and integrating for 4H, AB
pattern centered at 7.42 ppm and integrating for 4H, 6,56 (s, 2H,
Cp-H), 1.30 (s, 9H, t-Bu). .sup.13 C{H} NMR (C.sub.6 D.sub.6,
23.degree. C., 100 MHz): .LAMBDA. 151.7 (s), 132.6 (s), 130.9 (s),
127.2 (s, Ar C-H), 126.8 (s), 126.9(s), 126.6 (s, Ar C-H), 125.9
(s, Ar C-H), 125.1 (s, Ar C-H), 103.5 (s, Cp C-H), 34.7 (s,
C(CH3)3).
EXAMPLE 10
Preparation of Bis(2-(4-Tert-butylphenyl)indenyl)zirconium Dimethyl
(Catalyst G)
A solution of methyl lithium (1.4 M in diethyl ether, 315 mL, 0.44
mmol) was added dropwise to a solution of
bis(2-(4-tert-butylphenyl)indenyl)zirconium dichloride (0.140 g,
0.21 mmol) in diethyl ether (10 mL) at -78.degree. C. The yellow
solution was warmed to ambient temperature. After 20 min, the
solution turned colorless and then was stirred for an additional 2
hours after which time the solvent was removed in vacuo. The
product was recrystallized from hexane at -18 C. Yield: 79 mg
(60%). .sup.1 H NMR (C.sub.6 D.sub.6, 23.degree. C., 400 MHz):
.LAMBDA. 7.37 (m, 8H); 6.99 (m, 8H); 6.16 (s, 4H, Cp-H); 1.30 (s,
18H, t-Bu); -0.77 (s, 6H, CH.sub.3). .sup.13 C NMR (C.sub.6
D.sub.6, 23.degree. C., 100 MHz): .LAMBDA. 151.0 (s); 132.4 (s);
129.3 (s); 126.2 (dd, J.sub.C-H =157 Hz, .sup.2 J.sub.C-H =6 Hz,
aromatic C-H); 125.9 (dd, J.sub.C-H =156 Hz, .sup.2 J.sub.C-H =6
Hz, aromatic C-H); 125.0 (brd, J.sub.C-H =160 Hz, aromatic C-H);
124.83 (brd, J.sub.C-H =160 Hz, aromatic C-H); 124.78 (s); 98.3
(dd, J.sub.C-H =172 Hz, J.sub.C-H =6 Hz, Cp C-H); 36.3 (q,
J.sub.C-H =119 Hz, Zr(CH.sub.3).sub.2); 34.7 (s,
C(CH.sub.3).sub.3); 31.4 q,J.sub.C-H =121 Hz,
C(CH.sub.3).sub.3).
EXAMPLE 11
Preparation of 2-(4-Trifluoromethylphenyl)indene (Ligand 4)
A 3-neck 250-mL round-bottomed flask fitted with a condenser and an
addition funnel was charged with 1.36 g (56 mmol) of Mg turnings
and 17 mL of anhydrous diethyl ether. Slow addition of a solution
of 10.0 g (44 mmol) of 4-trifluoromethylbromobenzene in diethyl
ether (85 mL), followed by refluxing for 30 min, gave a red-brown
solution of the aryl Grignard reagent (some precipitate was
visible). The solution was cooled to room temperature, filtered
over a plug of Celite and most of the solvent was removed in vacuo
from the filtrate (ca. 15 mL of Et.sub.2 O remained). Toluene (25
mL) was added and the solution cooled to 0.degree. C. whereupon a
solution of 2-indanone (4.4 g, 33 mmol) in toluene (50 mL) was
added dropwise to give an orange slurry. This mixture was warrned
to room temperature and stirred for an additional 45 min. After
cooling to 0.degree. C., it was quenched with 95 mL of water.
Hexane (75 mL) was added, and the reaction mixture neutralized with
5M HCl. The organic layer was separated, and the aqueous layer was
extracted with two 20-mL and one 10-mL portions of hexane. The
combined organic layers were washed with two 35-mL portions of
brine and dried over anhydrous magnesium sulfate. After filtration
over Celite, the solvent was removed in vacuo yielding
2-(4-trifluoromethyl)phenylindanol as a solid. 1H NMR (CDCl.sub.3,
23.degree. C., 200 MHz): .LAMBDA. 7.5-8 (m, 4H), 7-7.5 (m, 4H), AB
pattern centered at 3.43 ppm and integrating for 4H, 2.38 (s, 1H,
OH).
Under argon, this alcohol and p-toluenesulfonic acid monohydrate
(200 mg) were dissolved in toluene (100 mL) and the solution was
heated to reflux for 4 hours to afford 5.59 g (65%) of
2-(4-trifluoromethylphenyl)indene upon recrystallization from
diethyl ether at -18 C. .sup.1 H NMR (CDCl.sub.3, 23.degree. C.,
400 MHz): .LAMBDA. AB pattern centered at 7.68 ppm and integrating
for 4H, 7.51 (d, J=7 Hz, 1H), 7.45 (d, J=7 Hz, 1H), 7.35 (s, 1H),
7.32 (dd, 2J=7 Hz, 1H), 7.25 (dd, 2J=7 Hz, 1H), 3.81 (s, 2H).
.sup.13 C NMR (CDCl.sub.3, 23.degree. C., 100 MHz): .LAMBDA. 144.8
(s), 144.7 (s), 143.2 (s), 139.3 (s), 128.8 (d, J.sub.C-H =168 Hz),
126.8 (dd, J.sub.C-H =168 Hz, J.sub.C-H =7 Hz), 125.7 (dd,
J.sub.C-H =161 Hz, J.sub.C-H =7 Hz), 125.6 (d, J.sub.C-H =ca. 160
Hz), 25.5 (d, J.sub.C-H =ca. 160 Hz), 124.2 (q, J.sub.C-F =272 Hz,
CF.sub.3), 123.8 (dd, J.sub.C-H =ca. 160 Hz, J.sub.C-H =9 Hz, 121.5
(dd, J.sub.C-H =160 Hz, J.sub.C-H =9 Hz), 38.9 (td, J.sub.C-H =129
Hz, .sup.2 J.sub.C-H =7 Hz, CH.sub.2). C, H analysis: Anal. Found
(Calcd.): C, 74.05 (73.84); H, 4.1.5 (4.26).
EXAMPLE 12
Preparation of Bis(2-(4-Trifluoromethylphenyl)indenyl)zirconium
Dichloride, Catalyst H (Ligand 4)
N-Butyllithium (1-6 M in hexanes, 2.5 mL, 4.0 mmol) was added
dropwise to a suspension of 2-(4-(trifluoromethyl)phenyl)indene
(1.02 g, 3.9 mmol) in diethyl ether (10 mL). The yellow-orange
solution was stirred at ambient temperature for 20 min after which
time the solvent was removed in vacuo. In a drybox, to the
resulting green-white solid was added ZrCl.sub.4 (462 mg, 2.0
mmol). The solids were cooled to -78.degree. C. and methylene
chloride (50 mL) was slowly added. The yellow suspension was warmed
to room temperature and kept there overnight. The orange solution
was then filtered over a plug of Celite and the Celite was washed
with CH.sub.2 Cl.sub.2 until the washings were colorless (ca. 40
mL). The product was recrystallized from toluene at -18 C. Yield:
471 mg (35%). .sup.1 H NMR (C.sub.6 D.sub.6, 23.degree. C., 400
MHz): .LAMBDA. 7.36 (d, J=8 Hz, 4H); 7.12 (dd, J=6.5 Hz, J=3.1 Hz,
4H); 7.09 (d, J=8 Hz, 4H); 6.86 (dd, J=6.4 Hz, J=3 Hz, 4H); 6.21
(s, 4H, Cp-H). C, H analysis: Anal. Found(Calcd.): C, 56.42
(56.47); H, 3.00 (2.96).
EXAMPLE 13
Preparation of 2-(4-Methylphenyl)indene (Ligand 5)
A 3-neck 500-mL round-bottomed flask fitted with a condenser and an
addition funnel was charged with 2.66 g (0.11 mol) of Mg turnings
and 20 mL of anhydrous diethyl ether. Slow addition of a solution
of 15.0 g (0.09 mol) of 4-bromotoluene in diethyl ether (100 mL),
followed by refluxing for 30 min, gave an orange solution of the
aryl Grignard reagent. The solution was cooled to room temperature,
filtered over a plug of Celite and the solvent was removed in vacuo
from the filtrate. Toluene (40 mL) was added and the solution
cooled to 0.degree. C. whereupon a solution of 2-indanone (9.27 g,
0.07 mol) in toluene (70 mL) was added dropwise to give an orange
slurry. This mixture was warmed to room temperature and stirred for
an additional 3 hours. After cooling to 0.degree. C., it was
quenched with 150 mL of water. Hexane (150 mL) was added and the
reaction mixture neutralized with 5M HCl. The organic layer was
separated, and the aqueous layer was extracted with two 50-mL
portions of hexane. The combined organic layers were washed with
two 50-mL portions of brine and dried over anhydrous magnesium
sulfate. After filtration over Celite, the solvent was removed in
vacuo yielding 2-(4-methyl)phenylindanol as a solid.
Under argon, this alcohol and p-toluenesulfonic acid monohydrate
(200 mg) were dissolved in benzene (200 mL) and the solution was
heated to reflux for 2 hours. After cooling to room temperature,
the solvent was removed in vacuo and the product,
2-(4-methylphenyl)indene, was recrystallized from diethyl
ether/hexane. Yield: 7.17 g (50%). .sup.1 H NMR (CDCl.sub.3,
23.degree. C., 400 MHz): .LAMBDA. 7.56 (d, J=8 Hz, 2H); 7.49 (d,
J=8 Hz, 1H); 7.41 (d, J=7 Hz, 1H); 7.36-7.14 (overlapping signals
integrating for 5H); 3.80 (s, 2H, CH.sub.2); 2.40 (s, 3H,
CH.sub.3). .sup.13 C{H} NMR (CDCl.sub.3, 23.degree. C., 100 MHz):
.LAMBDA. 146.5 (s), 145.5 (s), 143.0 (s), 137.4 (s), 133.2 (s),
129.4 (s); 126.6 (s), 125.64 (s), 125.57 (s), 124.5 (s), 123.6 (s),
120.8 (s), 39.0 (s, CH.sub.2), 21.3 (s, CH.sub.3). C, H analysis:
Anal. Found (Calcd.): C, 93.25 (93.16); H, 7.00 (6.84).
EXAMPLE 14
Preparation of Bis(2-(4-Methylphenyl)indenyl)zirconium Dichloride,
Catalyst I (Ligand 5)
N-Butyllithium (1.6 M in hexanes, 4.2 mL, 6.7 mmol) was added
dropwise to a solution of 2-(4-methyl)phenyl)indene (1.323 g, 6.4
mmol) in Et.sub.2 O (20 mL). The red-orange solution was stirred at
ambient temperature for 30 min after which time the solvent was
removed in vacuo. In a drybox, to the resulting solid was added
ZrCl.sub.4 (0.754 g, 3.2 mmol). The solids were cooled to
-78.degree. C. and methylene chloride (60 mL) was slowly added. The
solution was warmed to room temperature and kept there overnight.
The resulting yellow-orange turbid solution was then filtered over
a plug of Celite and the Celite was washed with CH.sub.2 Cl.sub.2
until the washings were colorless (ca. 60 mL). The product was
recrystallized from CH.sub.2 Cl.sub.2 /hexane at -18.degree. C.
Yield: 577 mg (31%). .sup.1 H NMR (C.sub.6 D.sub.6, 23.degree. C.,
400 MHz): .LAMBDA. 7.36 (d, J=8 Hz, 4H); 7.11 (m, 4H); 7.02 (d, J=8
Hz, 4H); 6.92 (m, 4H); 6.43 (s, 4H, Cp-H); 2.17 (s, 6H, CH.sub.3).
C, H analysis (crystallizes with CH.sub.2 Cl.sub.2): Anal. Found
(Calcd.): C, 63.21 (63.46); H, 4.41 (4.42).
EXAMPLE 15
Preparation of 2-(3,5-Dimethylphenyl)indene (Ligand 6)
A 3-neck 500-mL round-bottomed flask fitted with a condenser and an
addition funnel was charged with 1.86 g (77 mmol) of Mg turnings
and 15 mL of anhydrous diethyl ether. Slow addition of a solution
of 9.9 g (53 mmol) of 3,5-dimethyl-bromobenzene in diethyl ether
(60 mL), followed by refluxing for 1 hour, gave an orange solution
of the aryl Gnrgnard reagent. The solution was cooled to room
temperature, filtered over a plug of Celite and the solvent was
removed in vacuo from the filtrate. Toluene (30 mL) was added and
the solution cooled to 0.degree. C. whereupon a solution of
2-indanone-(5.67 g, 43 mmol) in toluene (50 mL) was added dropwise
to give an orange slurry. This mixture was warmed to room
temperature and stirred for an additional 9 hours. After cooling to
0.degree. C., it was quenched with 100 mL of water. Hexane (150 mL)
was added and the reaction mixture neutralized with 5M HCl. The
organic layer was separated, and the aqueous layer was extracted
with two 40-mL portions of hexane. The combined organic layers were
washed with two 40-mL portions of brine and dried over anhydrous
magnesium sulfate. After filtration over Celite, the solvent was
removed in vacuo yielding 2-(3,5-dimethyl)phenylindanol as a very
viscous oil.
Under argon, this alcohol and p-toluenesulfonic acid monohydrate
(213 mg) were dissolved in benzene (100 mL) and the solution was
heated to reflux for 2 hours. After cooling to room temperature,
the solvent was removed in vaczio and the product,
(3,5-dimethylphenyl)indene, was recovered by sublimation
(120.degree. C., high vacuum). Yield: 3.51 g (37%). .sup.1 H NMR
(CDCl.sub.3, 23.degree. C., 400 MHz): .LAMBDA. 7.52 (d, J=7 Hz,
1H); 7.44 (d, J=7 Hz, 1H); 7.4-7.1 (overlapping signals integrating
for 5H); 6.98 (s, 1H); 3.82 (s, 2H, CH.sub.2); 2.41 (s, 6H,
CH.sub.3). .sup.13 C NMR (CDCl.sub.3, 23.degree. C., 100 MHz):
.LAMBDA. 146.7 (s), 145.5 (s), 143.1 (s), 138.1 (s), 135.8 (s),
129.3 (d, J.sub.C-H =155 Hz), 126.5 (dd, J.sub.C-H =159 Hz,
J.sub.C-H =7 Hz), 126.2 (d, J.sub.C-H =165.Hz), 124.6 (dd,
J.sub.C-H =159 Hz, J.sub.C-H =7 Hz), 123.6 (d, J.sub.C-H =155 Hz),
123.5 (d, J.sub.C-H =156 Hz), 120.8 (dd, J.sub.C-H =159 Hz,
J.sub.C-H =8 Hz), 39.1 (td, J.sub.C-H =129 Hz, .sup.2 J.sub.C-H =6
Hz, CH.sub.2), 21.4 (q, J.sub.C-H =156 Hz, CH.sub.3). C, H
analysis: Anal. Found (Calcd.): C, 92.88 (92.68); H, 7.32
(7.32).
EXAMPLE 16
Preparation of Bis(2-(3,5-Dimethylphenyl)indenyl)zirconium
Dichloride, Catalyst J, (Ligand 6)
N-Butyllithium (1.6 M in hexanes, 2.8 mL, 4.5 mmol) was added
dropwise to a solution of 2-(3,5-dimethyl)phenyl)indene (0.945 g,
4.3 mmol) in diethyl ether (10 mL). The yellow-orange solution was
stirred at ambient temperature for 45 min after which time the
solvent was removed in vacuo. In a drybox, to the resulting clear
yellow solid was added ZrCl.sub.4 (0-504 g, 2.2 mmol). The solids
were cooled to -78.degree. C. and methylene chloride (50 mL) was
slowly added. The yellow suspension was warmed to room temperature
and kept there overnight. The resulting brown-orange solution was
then filtered over a plug of Celite and the Celite was washed with
CH.sub.2 Cl.sub.2 until the washings were colorless (ca. 40 mL).
The product was recrystallized from toluene at -18.degree. C.
Yield: 642 mg (50%). .sup.1 H NMR (C.sub.6 D.sub.6, 23.degree. C.,
400 MHz): .LAMBDA. 7.22 (s, 4H); 7.19 (m, 4H); 7.00 (m, 4H); 6.85
(s, 2H); 6.50 (s,4H, Cp-H); 2.27 (s, 12H). .sup.13 C NMR (C.sub.6
D.sub.6, 23.degree. C., 100 MHz): .LAMBDA. 138.2 (brs); 133.9 (s);
133.2 (brs); 130.5 (brd, J.sub.C-H =ca. 157 Hz); 127.0 (brs); 126.7
(dd, J.sub.C-H =163 Hz, .sup.2 J.sub.C-H =8 Hz, aromatic C-H);
125.24 (d, J.sub.C-H =ca. 163 Hz, aromatic C-H); 125.16 (dt,
J.sub.C-H =162 Hz, .sup.2 J.sub.C-H =6Hz, aromatic C-H); 103.9 (dd,
J.sub.C-H =175 Hz, .sup.2 J.sub.C-H =7 Hz, Cp C-H); 21.4 (q,
J.sub.C-H =127 Hz, CH.sub.3). C, H analysis: 20 Anal. Found
(Calcd.): C, 68.13 (67-98); H, 5.65 (5.03).
EXAMPLE 17
1-Methyl-2-phenylindene (Ligand 7)
Butyllithium (2.5 M in hexanes, 3.0 mL, 7.6 mmol was added dropwise
to a suspension of 2-phenylindene (1.382 g, 7.2 mmol) in THF (50
mL) at -78 C. Upon addition of n-butyllithium the reaction mixture
turned a dark orange color and 2-phenylindene dissolved. When the
addition of the reagents was complete the solution was allowed to
warm to room temperature and stirred for 30 minutes. CH.sub.3 I
(1.3 mL, 22 mmol) was added to this solution dropwise and the light
brown reaction mixture was heated to 40.degree. C. and stirred for
24 hours. After that the solvents were removed in vacuo and the
light brown solid was recrystallized from EtOH (25 mL) at room
temperature affording white needles (1.075 g, 75% yield). .sup.1 H
NMR (CDCl.sub.3, 20.degree. C., 300 MHz): .LAMBDA. 7.52-7.19
(overlapping signals from aromatic protons, 9H), 3.74 (s, 2H), 2.31
(s, 3H). .sup.13 C {.sup.1 H} NMR (CDCl.sub.3, 20.degree. C., 75
MHz): .delta..quadrature.1147.49 (C), 142.42 (C), 140.31 (C),
137.56 (C), 134.70 (C), 128.37 (CH), 128.24 (CH), 126.63 (CH),
126.40 (CH), 124.74 (CH), 123.32 (CH), 119.11 (CH), 40.96
(CH.sub.2), 11.94 (CH.sub.3).
EXAMPLE 18
Rac-bis(1-Methyl-2-phenylindenyl)zirconium Dichloride (Catalyst K,
Ligand 7)
Butyllithium (2.5 M in hexanes, 6.7 mL, 17 mmol) was added dropwise
to the solution of 1-methyl-2-phenylindene (3.447 g, 17 mmol) in
THF (50 mL) at -78.degree. C. As the deprotonation of the indene
occurred the solution changed from colorless to dark yellow. When
the addition was complete the solution was slowly warmed to room
temperature, stirred for 30 min, and then evaporated to dryness.
Toluene (50 mL) was added to the resulting yellow solid. The
resulting suspension was combined with ZrCl.sub.4 (1.974 g, 8.4
mmol) suspended in toluene (70 mL). The reaction mixture stirred at
40 C for 24 h. The turbid lemon yellow solution was cooled to room
temperature and filtered through a frit packed with Celite. The
Celite layer was washed with toluene (3.times.30 mL). The filtrates
were evaporated to dryness. The resulting yellow solid (3.536 g,
65% yield) contained rac-bis(1-methyl-2-phenylindenyl)zirconium
dichloride (Catalyst K) and
meso-rac-bis(1-methyl-2-phenylindenyl)zirconium dichloride
(Catalyst M) in 60:40 ratio. Repeated crystallization from
THF/pentane (4:1) gave Catalyst K as yellow rods (610 mg, 11%).
Spectroscopic data for Catalyst K: .sup.1 H NMR (20.degree. C.,
CDCl.sub.3, 300 MHz): .delta..quadrature.7.56 (t, J=7.2 Hz, 4H),
7.45 (m, 8H), 7.26 (t, J=7.6 Hz, 2H), 7.05 (t, J=7.6 Hz, 2H), 6.85
(d, J=8.6 Hz, 2H), 6.06 (s, 2H), 2.52 (s, 6H); .sup.13 C NMR
(CDCl.sub.3, 20 C, 75 MHz): .delta..quadrature.134.03 (C), 130.68
(C), 129.05 (CH), 128.70 (CH), 128.35 (C), 128.22 (CH), 126.64
(CH), 126.17 (CH), 125.17 (C), 124.74 (CH), 123.67 (CH), 120.91
(C), 98.64 (CH), 12.75 (CH.sub.3). Anal. Found (Calcd): C, 67.26
(67.11); H, 4.86 (4.58).
EXAMPLE 19
Meso-bis(1-Methyl-2-phenylindenyl)zirconium Dichloride (Catalyst L,
Ligand 7)
Repeated crystallization of the mixture from Example 19 from
CH.sub.2 Cl.sub.2 produced orange cubes of Catalyst M (554 mg,
10%). Spectroscopic data for Catalyst M: .sup.1 H NMR (20.degree.
C., CDCl.sub.3, 300 MHz): .delta. 7.49 (d, J=8.5 Hz, 2H), 7.34 (m,
11H), 7.19 (m, 5H), 6.07 (s, 2H), 2.57 (s, 6H); .sup.13 C NMR
(CDCl.sub.3, 20.degree. C., 75 MHz): .delta. 133.61 (C), 133.51
(C), 129.31 (C), 128.12 (CH), 128.24 (CH), 127.85 (CH), 125.90
(CH), 125.43 (CH), 124.39 (CH), 123.88 (C), 123.84 (CH), 119.24
(C), 97.87 (CH), 12.64 (CH.sub.3). Anal. Found (Calcd): C, 66.81
(67.11); H, 4.66 (4.58).
EXAMPLE 20
(Pentamethylcyclopentadienyl)(2-phenylindenyl)zirconium Dichloride
(Catalyst M)
Butyllithium (2.0 M in pentane, 3.9 mL, 7.8 mmol) was added
dropwise to a suspension of 2-phenylindene (1.441 g, 7.5 mmol) in
THF (30 mL) at -78.degree. C. As the deprotonation of
2-phenylindene occurred all of it dissolved to give dark orange
solution of the lithium salt. When the addition of the reagents was
complete the solution was gradually warmed to room temperature,
stirred for 30 minutes and then evaporated to dryness. The
resulting yellow solid was combined with Cp*ZrCl.sub.3 (2.500 g,
7.5 mmol) and toluene (40 mL). The mixture was heated to 60.degree.
C. and stirred for 36 h. The turbid yellow solution was filtered
through a glass frit packed with Celite. The Celite layer was
washed with toluene (3.times.10 mL). The combined filtrates were
evaporated to dryness. The solid was dissolved in CH.sub.2 Cl.sub.2
(15 mL) and the resulting solution was carefully layered with
pentane (40 mL). The layered solution was placed in a -18.degree.
C. freezer and light yellow crystals formed overnight (0.974 g, 25%
yield). .sup.1 H NMR (CDCl.sub.3, 20.degree. C., 300 MHz): .delta.
7.78 (d, J=7.1 Hz, 2H), 7.52 (dd, J=6.4 Hz, J=2H), 7.44 (t, J=7.2
Hz, 2H), 7.35 (t, J=7.3 Hz, 1H), 7.22 (dd, J=6.5 Hz, J=3.1 Hz, 2H),
6.87 (s, 2H), 1.84 (s, 15H). .sup.13 C{.sup.1 H} NMR (CDCl.sub.3,
20.degree. C., 75 MHz): .delta. 132.61 (C), 131.84 (C), 128.41
(CH), 128.37 (CH), 128.12 (CH), 127.19 (C), 126.22 (CH), 124.99
(C), 124.32 (CH), 103.64 (CH), 12.34 (CH.sub.3). Anal. Found
(Calcd): C, 61.27 (61.45); H, 5.31 (5.36).
EXAMPLE 21
(Pentamethylcyclopentadienyl)(1-methyl-2-phenylindenyl)zirconium
Dichloride (Catalyst N)
Butyllithium (2.5 M in hexanes, 3.8 mL, 9.5 mmol) was added
dropwise to the solution of 1-methyl-2-phenylindene (1.860 g, 9.0
mmol) in THF (20 mL) at -78 C. Upon the deprotonation of the indene
the solution became dark yellow. When the addition was complete the
solution was slowly warmed to room temperature, stirred for 30 min
and then evaporated to dryness. The resulting dark yellow solid was
combined with Cp*ZrCl.sub.3 (3.0 g, 9.0 mmol) and toluene (50 mL).
The mixture was heated to 70 C and stirred for 12 h. The resulting
turbid yellow solution was cooled to room temperature and filtered
through a glass frit packed with Celite. The Celite layer was
washed with toluene (5.times.25 mL). The combined filtrate and
washings were concentrated to a volume of 20 mL and a yellow
powdery solid precipitated out of solution. The mother liquor was
decanted and the product dried in vacuo (1.5 g , 38%). Yellow
rod-like crystals suitable for X-ray analysis were obtained from
THF/pentane solution at -18 C. .sup.1 H NMR (CDCl.sub.3, 20.degree.
C., 300 MHz): .delta..quadrature.7.50 (t, J=6.84, 2H), 7.33 (m,
6H), 7.04 (t, J=7.6 Hz, 1H), 6.46 (s, 1H), 2.54 (s, 3H), 1.79 (s,
15H). .sup.13 C NMR (CDCl.sub.3, 20.degree. C., 75 MHz): .delta.
133.06 (C), 131.49 (C), 130.85 (C), 130.14 (CH), 128.32 (CH),
127.94 (CH), 126.29 (CH), 126.03 (CH), 124.39 (CH+C), 122.82 (C),
122.61 (CH), 121.99 (C), 95.49 (CH), 12.27 (CH.sub.3, Cp*), 11.86
(CH.sub.3). Anal. Found (Calcd): C, 62.13 (62.13); H, 5.80
(5.61).
EXAMPLE 22
(Pentamethylcyclopentadienyl)(1-methyl-2-phenylindenyl)dimethyl
Zirconium (Catalyst O)
Methyllithium (1.4 M in diethyl ether, 2.0 mL, 2.8 mmol) was added
dropwise to the suspension of Catalyst 0 (0.692 g, 1.4 mmol) in
diethyl ether (20 mL) at -60.degree. C. The reaction vessel was
wrapped with aluminum foil and allowed to warm to room temperature.
The reaction mixture was stirred for 2 hours during which time its
color changed from bright yellow to white. Then mixture was
evaporated to dryness and toluene (20 mL) was added to the
resulting white solid. The turbid off white solution was filtered
through a glass fiit packed with Celite to give a clear solution,
which was evaporated to dryness and recrystallized from hexane (25
mL) at -18.degree. C. producing light yellow crystals (0.265 g, 42%
yield). .sup.1 H NMR (CD2Cl.sub.2, 20.degree. C., 300 MHz): .delta.
7.27 (d, J=8.6 Hz, 1H), 7.10 (m, 7H), 6.85 (d, J=7.6 Hz, 1H), 6.65
(t, J=7.1 Hz, 1H), 2.28 (s, 3H), 1.34 (s, 15H), -0.87 (s, 3H),
-2.10 (s, 3H). .sup.13 C NMR (CD2Cl.sub.2, 20.degree. C., 75 MHz):
.delta. 135.17 (C), 131.23 (C), 129.72 (CH), 128.49 (CH), 128.15
(C), 127.55 (CH), 124.18 (CH), 124.15 (CH), 123.73 (CH), 123.46
(CH), 123.18 (C), 117.92 (C), 112.83 (C), 91.22 (CH), 37.46
(CH.sub.3), 11.62 (CH.sub.3), 11.50 (CH.sub.3, Cp*). Anal. Found
(Calcd): C, 73.12 (72.83); H, 7.41 (7.42).
EXAMPLE 23
(Cyclopentadienyl)(2-phenylindenyl)zirconium Dichloride (Catalyst
P)
Butyllithium (2.5 M in hexane, 4.4 mL, 11 mmol) was added dropwise
to a suspension of 2-phenylindene (2.022 g, 11 mmol) in THF (40 mL)
at -78.degree. C. The mixture turned orange and became homogeneous.
It was gradually warmed to room temperature, stirred for 60 min,
and then evaporated to dryness. The resulting orange solid was
combined with CpZrCl.sub.3 (2.763 g, 11 mmol) and toluene (70 mL).
The reaction mixture was stirred at 30 C for 24 hours. The turbid
yellow solution was filtered through a glass frit packed with
Celite to give a brown solution. The Celite layer was washed with
toluene (20 mL). The combined filtrates were evaporated to dryness.
An .sup.1 H NMR spectroscopic analysis showed that the resulting
green-yellow solid contained a mixture of Catalyst P and Catalyst
A. Repeated crystallization from a concentrated toluene solution at
-18.degree. C. produced pure Catalyst P (0.420 mg, 9% yield).
.sup.1 H NMR (20.degree. C., CDCl.sub.3, 300 MHz): .delta. 7.71 (d,
J=7.2 Hz, 2H), 7.64 (dd, J=6.5 Hz, J=3.0 Hz, 21), 7.49 (t, J=7.3
Hz, 2H), 7.38 (t, J=7.2 Hz, 1H), 7.30 (dd, J=6.5 Hz, J+3.0 Hz, 2H),
6.92 (s, 2H), 6.10 (s, 5H). .sup.13 C NMR (CDCl.sub.3, 20.degree.
C., 75 MHz): .delta. 134.8 (C), 133.3 (C), 129.0 (CH), 128.9 (CH),
127.2 (C), 126.7 (CH), 126.4 (CH), 125.1 (CH), 116.7 (CH), 100.9
(CH). Anal. Found (Calcd): C, 57.16 (57.40), H, 3.67 (3.85).
EXAMPLE 24
Preparation of Bromo-3,5-di-t-Butylbenzene
1,3,5-Tri-t-butylbenzene (150 g, 0.6 mol) was dissolved in carbon
tetrachloride (300 mL) in a three-necked flask which had been
painted black to avoid light and equipped with an overhead stirrer,
thermometer and addition funnel under argon. Iron pellets (36 g,
0.64 mol) were added and the slurry was cooled to 5.degree. C.
t-Butylcatechol (1.0 g) was added and a solution of bromine (201.6
g, 1.26 mol) in carbon tetrachloride (75 mL) was added over a one
hour period. The slurry was stirred for an additional 4 hours at
5.degree. C. and quenched by pouring into ice water. The layers
were separated and the organics washed with 10% sodium hydroxide
solution. The solution was then washed with salt brine and dried
over magnesium sulfate. The solvent was evaporated and the product
was distilled under vacuum twice to give 75 g of product which was
then recrystallized from heptane to give 47 g of pure product
(29%).
EXAMPLE 25
Preparation of 2-(3,5-di-t-Butylphenyl)indene (Ligand 8)
1-Bromo-3,5-di-t-butylbenzene (47.2 g, 0.175 mol) was dissolved in
ether (500 mL) and cooled to -70.degree. C. t-Butyllithium (200 mL
of 1.7 M solution in pentane, 0.34 mol) was added at -70.degree. C.
over a two hour period. The solution was allowed to warm to room
temperature slowly. Magnesium bromide etherate (46.5 g, 0.18 mol)
was added and the slurry was stirred for one hour. The mixture was
then cooled to 5.degree. C. and 2-bromoindene (34.2 g, 0.18 mol)
was added. The mixture was warmed to room temperature and then
refluxed for three hours. The solution was cooled to room
temperature and the reaction was quenched carefully with water. The
layers were separated and the organics washed with salt brine and
dried over magnesium sulfate. The solvents were evaporated and the
product was distilled twice and recrystallized from hexane to give
37.1 g of product (70%).
EXAMPLE 26
Preparation of Bis(2-(3,5-di-t-Butylphenyl)indenyl)zirconium
Dichloride (Catalyst Q)
2-(3,5-Di-t-butylphenyl)indene (13.8 g, 0.045 mol), and anhydrous
diethyl ether (250 mL) were placed in a 1 L three-necked flask
under argon. n-Butyllithium (28 mL of a 1.6 M solution in hexanes,
0.045 mol) was added over a thirty minute period at 0.degree. C.
The solution was stirred for an additional two hours. Zirconium
tetrachloride (5.1 g, 0.022 mol), was added incrementally over a
one hour period. The mixture was then stirred overnight. The
ethereal solution was chilled to -10.degree. C. and the solids were
collected. The solids were taken up in 300 mL of dichloromethane
and the residual solids were removed by filtration through celite.
The celite was washed with an additional 100 mL of dichloromethane,
and the solvents were evaporated to give 11.2 g of product
(64%).
EXAMPLE 27
Preparation of Bis(2-(3,5-di-t-Butylphenyl)indenyl)hafnium
Dichloride (Catalyst R)
2-(3,5-Di-t-butylphenyl)indene (23.3 g, 0.077 mol), and anhydrous
diethyl ether (250 mL) were placed in a 1 L three-necked flask
under argon. n-Butyl lithium (48 mL of a 1.6 M solution in hexanes,
0.077 mol) was added over a thirty minute period at 0.degree. C.
The solution was stirred for an additional two hours. Hafnium
tetrachloride (12.2 g, 0.038 mol), was added incrementally over a
one hour period. The mixture was then stirred overnight. The
ethereal solution was chilled to -10.degree. C. and the solids were
collected by filtration. The solids were taken up in 300 mL of
dichloromethane and the residual solids were removed by filtration
through celite. The celite was washed with an additional 100 mL of
dichloromethane, and the solvents were evaporated to give 23.5 g of
product (72%).
EXAMPLE 28
Preparation of 3,5-Bis(Trimethylsilyl)bromobenzene
1,3,5-Tribromobenzene (125 g, 0.4 mol), was dissolved in anhydrous
diethylether (1 L), and cooled to -70.degree. C. n-Butyllithium
(250 mL, 1.6 M in hexanes, 0.4 mol) was added dropwise over a
one-hour period keeping the temperature near -70.degree. C. The
solution was stirred for an additional 20 minutes at -70.degree. C.
and then warmed to -10.degree. C. over a two-hour period. The
solution was then recooled to -70.degree. C. and
trimethylchlorosilane (45 g, 0.4 mol) was added over a one hour
period. The solution was allowed to stir and warm to room
temperature overnight. The solution was cooled to -70.degree. C.
and an additional 0.4 mol n-butyl lithium was added over a one-hour
period. The resulting slurry was stirred for one hour at
-70.degree. C., warmed to -10.degree. C. over a two-hour period and
then recooled to -70.degree. C. An additional 0.4 mol of
trimethylchlorosilane was added and the slurry was allowed to warm
to room temperature overnight. The mixture was quenched with water
and the layers were separated. The organic layer was washed twice
with sodium bicarbonate solution and with salt brine then dried
over magnesium sulfate. The solvents were evaporated under vacuum
and the product distilled twice under vacuum to yield 85.2 g (70%)
of a colorless liquid. b.p. 100-105.degree. C. @ 0.5 mmHg.
EXAMPLE 29
Preparation of 2-(3,5-Bis(Trimethylsilyl)phenyl)indene (Ligand
9)
Magnesium turnings (6.8 g, 0.28 mol) and anhydrous THF (100 mL)
were placed in a three-necked flack under argon. A solution of
3,5-bis(trimethylsilyl)bromobenzene (85.2 g, 0.28 mol) in of THF
(100 mL) was added incrementally to the THF and magnesium mixture
keeping the temperature near reflux. The Grignard reaction started
immediately after the addition of the first increment. The
remaining solution was added over a one hour period. The resulting
slurry was refluxed for an additional 30 minutes. The solution was
cooled to 20.degree. C. and a solution of 2-indanone (36.7 g, 0.28
mol) in ether (100 mL) was added dropwise over a 1 hour period. The
solution was then stirred at room temperature overnight. The
solution was neutralized with 1N HCl. The aqueous layer was
separated and washed three times with 100 mL of ether. The organics
were combined and dried over magnesium sulfate. The solvents were
evaporated to yield a tan solid of the crude alcohol. This solid
was taken up in acetic acid (200 mL) and cooled to 15.degree. C. A
solution of sulfuric acid (40 g) and of acetic acid (200 mL) was
added slowly, keeping the temperature of the mixture near
15.degree. C. The product separated as and oil. The acetic acid
layer was diluted with 1 L of ice water and extracted with toluene.
The organic layer was separated and washed twice with sodium
bicarbonate solution and dried over magnesium sulfate. The solvents
were evaporated. The product was then taken up in a minimal amount
of hexanes and passed through a short silica gel column to remove
very polar material. Attempts to crystallize the product failed and
the product was distilled to yield 20.5 g (22% yield), b.p.
175-180.degree. C. @ 0.3 mm Hg. This procedure was repeated to
yield an additional 22.3 grams of material. .sup.1 H NMR (C.sub.6
D.sub.6): .delta. 7.45 (2H, s), 7.26 (1H, s), 7.13 (2H, dd), 6.94
(1H, m), 6.85 (2H, m), 3.51 (2H, s).
EXAMPLE 30
Preparation of Bis(2-(3,5-bis(Trimethylsilyl)phenyl)indenyl)
Zirconium Dichloride (Catalyst S)
2-(3,5-bis(trimethylsilyl)phenyl)indene (20.5 g, 0.061 mol), and
anhydrous diethyl ether (250 mL) were placed in a 1 L three-necked
flask under argon. n-Butyllithium (38 mL of 1.6 M hexane solution,
0.061 mol) was added over a thirty minute period at 0.degree. C.
The solution was stirred for an additional two hours. Zirconium
tetrachloride (7.0 g, 0.03 mol), was added incrementally over a one
hour period. The mixture was then stirred overnight. The ethereal
solution was chilled to -10.degree. C. and the solids were
collected. The solids were taken up in 300 mL of dichloromethane
and the residual solids were removed by filtration through celite.
The celite was washed with an additional 100 mL of dichloromethane,
and the solvents were evaporated to give 15.6 grams of product (62%
yield). .sup.1 H NMR (C.sub.6 D.sub.6): .LAMBDA. 7.75 (2H, s), 7.62
(1H, s), 6.62 (2H, m), 6.45 (2H, m), 6.41 (2H, s).
II. POLYMERIZATION
This section gives examples of polymer preparation using catalysts
of this invention, including the catalysts of our aforesaid U.S.
Pat. No. 5,594,080 and the novel catalysts disclosed herein and
compares them to bridged catalysts.
General Procedures: Olefin Polymerization
Method A: Propylene Polymerization in Toluene. In a nitrogen filled
drybox, a 300-mL stainless-steel Parr reactor equipped with a
mechanical stirrer was charged with dry methylaluminoxane (MAO Type
4 Akzo, dried >24 h) dissolved in toluene. A 50-mL pressure tube
was charged with the corresponding metallocene catalyst dissolved
in 20 mL of toluene. The reactor was purged several times by
pressurizing with propylene and venting. It was then brought to the
appropriate pressure (until saturation) and temperature with
stirring. The pressure tube containing the metallocene was
pressurized to 200 psi with nitrogen. Once the MAO solution was
saturated with propylene the catalyst solution was injected into
the reactor at the appropriate temperature. After stirring for 1
hour, the polymerization was quenched by injecting methanol (10
mL). The autoclave was then slowly vented and opened. The polymer
was precipitated by the addition of methanol (400 mL), collected by
filtration, and dried overnight at ambient temperature.
Method B: Bulk Polymerization of Propylene. A 300-mL stainless
steel Parr reactor equipped with a mechanical stirrer was
evacuated, purged 4-5 times with gaseous propylene by pressurizing
and venting and charged with liquid propylene (100 mL). The monomer
was equilibrated at the reaction temperature and the reaction was
initiated by injecting the subject zirconocene/MAO solution in
toluene (20 mL) under Ar pressure (250 psig, 1720 kPa). The
reaction was run until a slight drop in pressure (1-2 psig, 7-14
kPa) was registered for 25-50 minutes and then quenched by
injecting MeOH (20 mL). The reactor was slowly vented and opened.
The polymer was precipitated in acidified MeOH (5% HCl), filtered
and dried in a vacuum oven at 40.degree. C. to constant weight.
Method C: Ethylene Homopolymerization in Toluene Solution. A 300-mL
stainless steel Parr reactor equipped with a mechanical stirrer was
charged with dry methylaluminoxane and toluene (80 mL). A 50-mL
pressure tube was charged with the zirconocene solution in toluene
(20 mL). The reactor was purged with ethylene 34 times by
pressurizing and venting. The monomer was then equilibrated with
the toluene in the reactor for 30 min at the polymerization
temperature and pressure with constant stirring. The pressure tube
with the metallocene solution was pressurized to 200 psig (1400
kPa) with argon and the solution was injected into the reactor.
After 1 h the reaction was quenched by injecting methanol (20 mL).
The reactor was slowly vented and opened. The polymer was collected
by filtration and dried in a vacuum oven at 40.degree. C. to
constant weight.
Method D: Propylene Polymerization in Toluene Solution in the
Presence of Ethylene-(PRE effect). A 4-L stainless steel cylinder
was filled with ethylene and propylene at a certain ratio measured
from the partial pressures of the two gases. The gas mixture was
heated to 100.degree. C. for 20 hours to facilitate gas mixing. The
mixture was used for 2 polymerizations and then the cylinder was
refilled with a new mixture.
In a nitrogen filled drybox, a 300-mL stainless steel Parr reactor
equipped with a mechanical stirrer was charged with dry
methylaluminoxane and 80 mL of toluene. A 50-mL pressure tube was
charged with the zirconocene solution in toluene (20 mL). The
reactor was purged 4-5 times with ethylene-propylene mixture by
pressurizing and venting. The gas mixture was then equilibrated
with the toluene in the reactor for 15 min at 15 psig (100 kPa) and
20.degree. C. with constant stirring. The pressure tube with the
metallocene solution was pressurized to 200 psig (1400 kPa) with
argon and the reaction was started by injecting the catalyst. The
reaction was run for 15 minutes with constant stirring and was
quenched by injecting 20 mL of methanol. The reactor was then
slowly vented and opened. The polymer was precipitated in acidified
MeOH (5% HCl), filtered, washed with MeOH and dried in a vacuum
oven at 40.degree. C. to constant weight.
Method E: Polymerization in Liquid Propylene. A 300-mL stainless
steel Parr reactor equipped with a mechanical stirrer was
evacuated, purged 4-5 times with gaseous propylene by pressurizing
and venting and charged with liquid propylene (100 mL). Propylene
was cooled down to the reaction temperature and overpressurized
with ethylene to a certain pressure. The monomer mixture was
equilibrated at the reaction temperature under constant ethylene
pressure for at least 10 minutes. Immediately prior to the catalyst
injection the ethylene line was disconnected and the reactor was
cooled to 2-3.degree. C. below the reaction temperature to
compensate for the exothermic effect upon initiation.
Zirconocene/MAO solution in toluene (20 mL) was pressurized with Ar
to approximately 120 psi above the total pressure in the reactor).
In the case of polymerizations at 0-2.degree. C. the catalyst was
cooled down in an ice bath and then injected. In the case of
polymerizations at 20.degree. C. the catalyst solution at room
temperature was injected. The ethylene line was reconnected and the
reaction was run for 15-60 min at constant total pressure and
temperature. The reaction was quenched by injecting MeOH (20 mL),
the reactor was slowly vented and opened. The polymer was
precipitated in acidified MeOH (5% HCl), filtered, washed with MeOH
and dried in a vacuum oven at 40.degree. C. to constant weight.
Method F: Polymerization in Liquid Propylene With Ethylene (PRE and
EPE). To a 19 gallon (72 liter) reactor the following material is
charged: 20.4 kg polymer grade propylene, 0.23 kg cthylenc and 9.07
kg heptane after being passed over guard columns to remove moisture
and dissolved oxygen. The reactor then is heated to 43.3.degree.
C., while stirring. In a dry box, 0.09 gram of metallocene catalyst
Q is dissolved in 50 grams of toluene and added to 40 grams of PMAO
(10.6% Al), stirred and added to a hoke cylinder. Toluene (50
grams) is used to wash the reagent remnants from the glassware into
the hoke cylinder. The catalyst/cocatalyst solution is aged for a
total of 30 minutes before being added to the reactor. At reactor
temperature of 43.3.degree. C., the catalyst is injected to
initiate the polymerization. The termperature is allowed to
increase to 48.9.degree. C. and maintained for 3 hours. During the
polymerization, 45-gram aliquots of ethylene are added every 20
minutes for a total of 590 grams of ethylene (including the initial
charge). The heat of reaction is removed by evaporative cooling as
well as via a reactor cooling jacket. At the end of the 3 hours,
the reactor pressure is reduced to atmospheric to rapidly flash
unreacted propylene and ethylene. A make up solvent, such as
heptane or toluene is added to redissolve the polymer. The polymer
is recovered by methanol coagulation, washed and dried to yieled
12.9 lbs of copolymer product with MFR of 1.9 g/10 min., ethylene
content of 8 mole %, and Mn=119,000, Mw=358,000, Mw/Mn=3.0 (by GPC
analysis).
III. ANALYTICAL METHODS
Molecular weight data are obtained on a Waters 150.degree. C. GPC
instrument at 139.degree. C. using 0.07% (wt/vol) solutions of the
polymer in 1,2,4-trichlorobenzene using isotactic polypropylene and
polyethylene as reference standards.
Isotacticity data for polypropylene was obtained from .sup.3 C NMR
at 130.degree. C. with a Varian Unity 500 MHz NMR spectrometer
operating at 125 MHz, a Varian XL400 MHz NMR spectrometer operating
at 100 MHz, or a Varian UI 300 (10 mm tubes) operating at
100.degree. C. Samples are run either as solutions of 0.25 g
polymer in 2.6 mL dideuterotetrachloroethane, as 0.05 g polymer in
0.5 mL dideuterotetrachloroethane, or as a 10-12% w/w sample in
1,2,3,3-tetrachloroethane/10 vol. % 1,1,2,2-tetrachloroethane-d2.
Acquisition time of 1 second with no additional delay between
pulses and continuous proton decoupling were used. Sample
concentration was 10-12 weight percent. All spectra were referenced
using the solvent peak. The areas of the peaks in the methyl region
determined from the spectral integrations were used to determine
the isotacticity of the polymer.
Isotacticity data for ethylene-propylene copolymers was determined
from .sup.13 C NMR performed on a Varian UT 300 in a 10 mm
switchable broad band probe at 140.degree. C. in
o-dichlorobenzene/10 vol. % benzene-d6 as a solvent using gated
decoupling mode. Sample concentrations of 10-12 weight percent was
used. Acquisition time was set to 1 second with additional 12
second delays between pulses. Spectra were referenced to benzene-d6
peak. Spectral integrations were used to determine the copolymer
composition and monomer sequence distribution.
Thermal analysis was performed by DSC, using a TA/DuPont 2100
instrument, with nitrogen purge. Sample weight was about 13 mg.
Heating rate was 20.degree. C./min. Cooling rate was 10.degree.
C./min. Peak melting endotherm temperature (Tm) and heat of fusion
are typically reported from the second heat cycle. Heat of
crystallization and temperature of crystallization are typically
reported from the first cooling cycle.
Polymer Testing Methods
Mechanical property tests were conducted with stabilized samples in
which commercial antioxidants were mixed at conventional amounts,
as in the isotactic polypropylene art, before molding or extrusion.
Ultranox 641 (at 0.09%), Ultranox 210 (at 0.09%) and DHT-4A (at
0.02%) were employed in this application.
Melt flow rates are determined using a Tinius Olsen Melt Flow Meter
operating at 232.degree. C. according to ASTM method D1238. In a
typical experiment, 5 grams of the polymer sample is mixed with 50
mg of BHT and this mixture added to the heating chamber. A 2.0 Kg
mass is attached to a plunger inserted into the heating chamber and
the melt flow is determined by measuring the quantity of material
extruded over a period of 1 minute. Results are reported in units
of decigrams polymer/minute of flow, or grams/10 min by ASTM method
D1238.
Tensile, stress relaxation and hysteresis recovery/set tests were
performed with ASTM D 1708 dumbell specimens (0.9 inch gauge
length) die cut from extruded film or compression molded sheets.
Crosshead separation rate was 25.4 cm/min for the hysteresis test
and 51 cm/min. for the other tests.
Tensile Test: ASTM D 1708-95, ASTM D 638-96. Ultimate tensile
strength (i.e. stress at break) is reported. Tensile modulus is the
linear slope of the stress/strain plot at lowest elongation. In
polyolefins modulus, like density, is a measure of crystallinity.
Percent elongation to break is the ultimate elongation of the gauge
region of the specimen at failure (break). Percent elongation
(broken) is the residual set of the central 10 mm segment of the
gauge region measured immediately after break, and so is a measure
of recovery from highest elongation (ASTM D 412-92).
Stress Relaxation Test: ASTM E 328-96. The test specimen is
deformed to the specified elongation at the specified rate, and
then the decay of stress with time is measured while the specimen
is held at fixed elongation. Tensile stress relaxation is reported
as the decrease in stress during 5 minutes at 50% elongation
(1.5.times.original gauge). Lower percent stress relaxation
indicates better retention of recovery force during extended
deformation time which is generally associated with better
elastomer performance. However, stress decay occurs rapidly
initially (about 4/5 during the initial 30 seconds for elastomeric
polypropylene), and then decays asymptotically. Final set and
stress are also reported.
Hysteresis Test: The 100% elongation hysteresis test was performed
by extending the specimen to 2.times.original gauge length in three
successive cycles of extension and recovery, with 30 second hold at
100% elongation and 60 second hold after crosshead recovery between
cycles. In this hysteresis test, tensile set is reported as the
cumulative set from the first two extensions, measured as the
elongation at which stress exceeds the baseline on the third
extension. Stress relaxation is measured as the decrease in stress
(or force) during the 30 sec. that the specimen is held at
extension during the first cycle. Retained force is measured as the
ratio of stress at 50% elongation during the second cycle recovery
to the initial stress at 100% elongation during the same cycle.
Lower set indicates higher elongational recovery. Higher values of
retained force and lower values of stress relaxation indicate
stronger recovery force. Better general elastomeric recovery
properties are indicated by low set, high retained force and low
stress relaxation. In contrast, a flexible polymer is characterized
as one having above about 500% elongation, tensile modulus of below
about 100 MPa, but essentially no retained force (at the 50%
elongation point).
EXAMPLES 30, 31
Propylene Homopolymerization with Catalyst D
Polymerizations were carried out according to Method A and the
results are presented in Table 1.
TABLE 1 Propylene Polymerizations Using Complex D and MAO.sup.a.
Pressure M.sub.w.sup.e M.sub.w / [m].sup.f [mmmm].sup.f Example
psig (kPa) Productivity.sup.d (.times.10.sup.3) M.sub.n (%) (%)
30.sup.b 25 (170) 250 196 3.3 75 45 30.sup.c 35 (240) 500 243 3.2
78 51 .sup.a Conditions: [Al]/[Zr] = 1000, T = 25 C, t = 60 min.
.sup.b [Zr] = 5.5 .times. 10.sup.-5 M. .sup.c [Zr] = 5.0 .times.
10.sup.-5 M. .sup.d kg Polypropylene/mol. Zr/h. .sup.e Determined
by gel permeation chromatography versus polypropylene. .sup.f
Determined by .sup.13 C NMR spectroscopy.
EXAMPLES 32-48
Propylene Polymerization in the Presence of Ethylene
The processes of this invention include novel methods for
polymerizing alpha olefins to provide elastomeric, alpha olefin
polymers and copolymers, particularly propylene-ethylene (P-E)
copolymers. Unexpectedly, these processes also result in
significant increases in productivity and polymer molecular weight
evidencing. the PRE effect. Table 2 below shows the effect of
ethylene on polymerization in liquid propylene using catalysts A,
D, K, and M.
Viewing Table 2, in those polymerization systems containing
ethylene, we observe that productivity increases by approximately
an order of magnitude, as compared to those systems not containing
ethylene (Examples 32, 33, 35, 38, 41, 44 and 47). Further, a 3 to
4 fold increase in molecular weight is observed for those polymers
containing ethylene in percentages greater than about 14%. The
ethylene enhancement factors EEF=kpp[Mp]/(kpp.sup.h [Mp.sup.h ]
range from 2.2-7.8.
TABLE 2 Polymerizations In Liquid Propylene.sup.a Wt. % [cat]
t.sub.rxn T P.sub.total, Ex. EEF Cat. Additive Et. in feed M min
.degree. C. psig (kPa) X.sub.e.sup.b Productivity.sup.c
m.sub.2.sup.d M.sub.w.sup.e .times. 10.sup.-3 MWD.sup.e 32 -- A
none -- 1 25 0 76 (524) 0 11920 65 835 5.40 33 1 A E 7.3 1 25 0 111
(765) 30 25560 38 -- -- 34 -- A none -- 1 25 19 117 (807) 0 13200
60 549 3.49 35 -- A H.sub.2 -- 120 30 23 140 (965) 0 6800 -- -- --
36 2.2 A E, H.sub.2 0.6 120 60 23 140 (965) 2 15776 -- 408 3.7 37
3.2 A E 4.1 1 25 19 149 (1027) 25 69280 56 1789 2.62 38 -- D none
-- 1 25 0 74 (510) 0 6000 76 756 5.70 39 7.8 D E 5.2 1 25 1 102
(703) 18 64540 81 2386 3.41 40 6.7 D E 6.4 1 25 3 114 (786) 30
75970 80 2159 2.99 41 -- D none -- 1 25 19 116 (800) 0 8300 78 621
4.58 42 5.3 D E 3.1 1 25 19 141 (972) 14 58260 87 1776 5.60 43 4.8
D E 4.3 1 25 19 151 (1041) 18 60160 88 1901 2.42 44 -- K none -- 42
60 20 118 (814) 0 363 33 55.9 15.3 45 -- K E 3.7 42 30 6 100 (690)
24 3713 37 288 15.1 46 -- K E 6.2 42 30 20 162 (1117) 40 3715 30
99.5 14.7 47 -- M none -- 50 52 3 76 (524) 0 1900 63 597 4.52 48 --
M E 3.7 1.7 20 0 83 (572) 37 31670 73 1254 3.11 .sup.a Al/Zr =
3500-10000 .sup.b Xe = mole % ethylene incorporated into the
copolymer determined by .sup.13 C NMR .sup.c kg .multidot.
polymer/(mole .multidot. Zr .multidot. hr) .sup.d for copolymers,
m.sub.2 is defined as the ratio of the area of the first methyl
triplet over that of T .sup.e determined by high temperature
GPC
EXAMPLES 49-52
These examples show polymerizations in a toluene solution (Method
D) with Catalyst L and Catalyst N. The results are presented in
Table 3 below.
TABLE 3 Polymerization in Toluene Solution with Catalysts L and
N..sup.a) P.sub.total Mw M.sub.w / Example Cat. % E.sub.gas psig
(kPa) X.sub.E.sup.b Prod..sup.c (.times.10.sup.3).sup.d M.sub.n 49
L 0 75 (520) 0 143 68 5.8 50 L 50.0 15 (100) 74.1 440 91 2.5 51 N 0
75 (520) 0 25 21 8.9 52 N 27.2 15 (100) 76.6 379 104 13.4 .sup.a)
Al/Zr = 1000, T = 20.degree. C. .sup.b X.sub.E = % ethylene
incorporated into the copolymer determined by .sup.13 C NMR; .sup.c
kg .multidot. polymer/(mole .multidot. Zr .multidot. hr) .sup.d
determined by high temperature GPC.
The copolymers of Examples 50 and 52, exhibit significantly high
productivities and molecular weights as compared to Examples 49 and
51, which were carried out in the absence of ethylene.
COMPARATIVE EXAMPLES 53-58
Polymerization with Bridged Ethylene bis (indenyl) ZrCl.sub.2
Polymerizations were carried out in liquid propylene (Method E)
with bridged ethylene bis (indenyl) ZrCl.sub.2 and the results are
presented in Table 4.
TABLE 4 Polymerizations with EBIZrCl.sub.2 in liquid
propylene.sup.a [cat], t.sub.rxn, T P.sub.total, Ex. EEF Additive M
min .degree. C. psig (kPa) X.sub.e.sup.b Productivity.sup.c
m.sub.2.sup.d M.sub.w .times. 10.sup.-3 MWD 53 N/A none 1 25 0 74
(510) 0 19100 92 98.3 2.13 54 <1 E 2 55 2 86 (590) 23 16457 100
78.1 2.14 55 1.7 E 1 30 1 102 (704) 40 106230 100 75.5 1.96 56 N/A
none 1 25 20 117 (807) 0 86400 92 70.6 1.98 57 <1 E 1 25 19 152
(1050) 42 45580 100 69.7 2.01 58 1.0 E 1 25 20 144 (993) 39 243240
100 67.2 2.03 .sup.a Al/Zr = 3500-10000 .sup.b Xe = mole % ethylene
incorporated into the copolymer determined by .sup.13 C NMR .sup.c
kg .multidot. polymer/(mole .multidot. Zr .multidot. hr) .sup.d
determined by high temperature GPC
As these comparative examples show, there is very little effect of
ethylene on the bridged catalysts ethylene bis (indenyl)
ZrCl.sub.2. In example 54 and 57, lower productivities were
observed. Only in example 55 was a small ethylene effect observed,
but this is at a polymerization temperature of 2.degree. C., which
is impractical for commercial practice.
EXAMPLES 59-66
Reactivity Ratios for Ethylene-Propylene Copolymerization
Polymerization were carried out by Method E and the results are
presented in Table 5.
TABLE 5 Reactivity Ratios for Ethylene-Propylene Copolymerization T
Xe/Xp Xe in Ex. Cat. .degree. C. N.sub.exp.sup.a in feed.sup.b
polymer.sup.c r.sub.e r.sub.p.sup.d r.sub.e.sup.d r.sub.p.sup.d
r.sub.p /r.sub.e 59 A 1 5 0.06-0.22 21-44 0.92 .+-. 0.08 3.8 .+-.
0.3 0.25 .+-. 0.01 0.066 60 A 20 5 0.06-0.16 23-45 1.3 .+-. 0.2 5.4
.+-. 0.9 0.24 .+-. 0.04 0.044 61 D 2 5 0.05-0.08 18-43 1.3 .+-. 0.1
4.2 .+-. 0.7 0.31 .+-. 0.03 0.074 62 D 20 5 0.05-0.08 14-22 1.9
.+-. 0.1 6.0 .+-. 0.2 0.33 .+-. 0.03 0.055 63 K 6 1 0.06 24 0.74
4.6 0.16 0.035 64 K 20 2 0.08-0.09 39-41 0.56 .+-. 0.01 5.3 .+-.
0.2 0.11 .+-. 0.01 0.021 65 EBIZrCl.sub.2 2 5 0.04-0.18 23-54 0.49
.+-. 0.03 5.4 .+-. 0.6 0.09 .+-. 0.01 0.017 66 EBIZrCl.sub.2 20 1
0.07 42 0.50 7.1 0.07 0.010 .sup.a number of experiments used for
the reactivity ratio determination .sup.b the range of the ratios
of the mole fractions of ethylene (Xe) and propylene (Xp) in the
feed .sup.c the range of E content to copolymers determined using
.sup.13 C NMR .sup.d determined using .sup.13 C NMR
COMPARATIVE EXAMPLES 67-71
Polymerization of Ethylene in Toluene Solution with Catalysts A, K,
L, M, and N
Polymerizations were carried out in toluene and the results are
presented in Table 6.
TABLE 6 Ethylene Polymerization.sup.a) Productivity kg .multidot.
PE Mw M.sub.w / Example Catalyst mol .multidot. Zr .multidot. hr
.times.10.sup.-3 M.sub.n 67 (2PhInd).sub.2 ZrCl.sub.2 A 3570 2040
3.2 68 rac-(1Me2PhInd).sub.2 ZrCl.sub.2 K 7280 1034 3.4 69
meso-(1Me2PhInd).sub.2 ZrCl.sub.2 L 3050 1966 4.0 70
Cp*(2PhInd)ZrCl2 M 3470 1883 4.0 71 Cp*(1Me2PhInd)ZrCl.sub.2 N 4810
1982 3.9 .sup.a) reaction conditions: PE = 25 psig, [Zr] = 5
.multidot. 10.sup.-6 M, t.sub.rxn = 1 hr, T = 20 .+-. 1.degree. C.,
[Zr]:[MAO] = 1:2750
EXAMPLES 72-79
Polymerization of Propylene with Catalysts E, Q, and S
Polymerizations were carried out in liquid propylene and the
results are presented in Table 7, Examples 72-75 in absence of
ethylene, and 76-79 in the presence of ethylene showing the PRE
effect. Polymer properties are presented in Table 8.
TABLE 7 Preparation of Elastomeric Polyolefins in Presence and
Absence of Ethylene. Press. NMR Wt. % E Zr cat. Temp psig Time
Yield Activity Wt. % E MFR.sup.a (mm) Ex Cat in feed (g) Al:Zr
(.degree. C.) (kPa) (hr) (g) (g/g .multidot. hr).sup.b in polymer
(g/10 min.) % 72 E 0 0.35 1100 37.0 180.0 (1241) 2.5 2494 2848 0.0
1.2 37.00 73 E 0 0.35 1100 38.0 180.0 (1241) 2.5 2444 2794 0.0 0.73
33.60 74 E 0 0.35 1100 38.0 180.0 (1241) 2.5 4752 5431 0.0 1.8
38.10 75 E 0 0.35 1100 38.0 180.0 (1241) 2.5 4441 5076 0.0 2.2
37.50 76 Q 1 0.015 1000 50.2 264.1 (1821) 1.0 223.0 15000 2.2 1.0
75.2 77 Q 1 0.015 1000 49.0 260.8 (1798) 1.0 496.6 33000 2.9 2.0
69.1 78 S 1.4 0.0152 1100 50.0 266.7 (1839) 1.0 231.4 15000 3.2 2.0
69.9 79 S 1.9 0.015 1100 50.2 274.8 (1895) 1.0 387.9 26000 3.3 1.8
66.3 .sup.a Melt Flow Rate (g/10 min) .sup.b grams polymer per gram
catalyst .times. hrs
TABLE 8 Properties of Polymers Made in Presence and Absence of
Ethylene Ex 72-75 without ET; Ex 76-79 with ET Elong. Mod- to
Stress.sup.b Strength ulus break Relax Set.sup.b Tm, Exmpl
MFR.sup.a (MPa) (MPa) (%) (%) (%) .degree. C. 72 1.2 12.3 8.92 827
38.9 7 149 73 0.73 12.6 6.72 830 38.6 6 148 74 2.0 13.8 9.57 819
40.5 10 -- 75 2.0 14.4 10.5 1010 39.7 11.8 -- 76 1.0 20.4 44.3 988
49.7 8.7 84-125 77 2.0 11.9 10.7 976 36.1 7.6 85-125 78 1.9 15.3
17.4 1006 39.6 7.5 103 79 1.8 10.2 8.26 1080 38.5 6.7 108 .sup.a
Melt flow rate (g/10 min). .sup.b 100% elongation.
EXAMPLES 80-85
Elastomeric Property Enhancement Effect (EPE Effect)
The general procedure of Method F was followed for Examples 80-85.
The reagent quantities, yields and reaction conditions are shown in
Table 9. Polymer composition and properties are shown in Table 10.
Examples 80 and 84 are comparative examples of homopolymers, in
which ethylene was not used as a co-monomer. A smaller (7.6 liter)
reactor was used for Example 84 so less reagents were used, but
procedures were essentially the same as the other examples.
Polymerization experiments were performed using commercially
available MAO solutions having 10.1 wt. % Al (Examples 80-83 and
85) or 9.6 wt. % Al (Example 84).
TABLE 9 Polymerization Run Parameters for Homo- and
Copolymerizations Time Temp. Catalyst MAO C.sub.3 C.sub.7 C.sub.2
Yield Productivity Example Metallocene (hrs) (.degree. C.) (g) (g)
[Al]/[Zr] (lbs) (lbs) (lbs) (lbs) (kg/g) 80 Q 2 49 0.3 100 1100 40
24 0 10 15 81 Q 2 55 0.2 100 1700 40 25 0.9 12.6 28 82 Q 2 45 0.3
101 1200 20 50 0.5 12 18 83 Q 2 48 0.2 88 1500 50 10 1.4 12.7 29 84
S 1 40 0.021 6.5 930 6 0 0 0.47 10 85 S 3 46 0.2 110 1900 50 22 0.7
18.3 41
TABLE 10 Polymer Property Data for Homo- and Copolymerizations
C.sub.2.sup.+ Hysteresis, 30 sec. hold % Stress (mole Tensile
Properties 100% Elongation Relax %) Mod- % % % % 5 min. in m.p. Mw/
NMR Strength ulus Elong. Elong. Stress Retained % 50% Examples
Polymer (.degree. C.) MFR Mw Mn (m2) m4 (MPa) (MPa) Broken at Break
Relax Force Set elongation Homopolymer/ Catalyst Q 80 0 144 12.5
228,000 3.3 (72.0) 56.2 16.7 40.3 164 610 46.3 0 39.9 61.7
Copolymer/ Catalyst Q 81 3.7 108 15.3 199,000 2.7 (64.6) -- 9.41
6.43 83 1174 38.9 26.3 7.8 50.2 82 4.0 103 10.3 220,000 3.1 (66.6)
-- 8.69 10.2 42 682 35.9 28.2 10.4 46.5 83 1.9 137 5.3 283,000 3.0
(70.7) -- 15.3 22 52 563 42.4 10.6 19.1 53.9 Homopolymer/ Catalyst
S 84 0 144 6.8 258,000 2.9 -- 62.1 20.1 95.7 348 800 45.5 0 48.1
60.2 Copolymer/ Catalyst S 85 3.3 118 4.9 281,000 2.8 (66.8) --
16.1 13.1 45 999 39.6 23.5 7.5 48.1
DISCUSSION OF EXAMPLES 33-79
The catalyst systems disclosed in in this invention and in U.S.
Pat. No. 5,594,080, included by reference herein polymerize
propylene to elastomeric polypropylenes with productivities which
range from 200-13,000 kg polymer/mol Zr hr (see Examples 30, 31,
32, 33, 35, 38, 41, 44, 47, 49 and 51). As evidence of the PRE
effects, addition of ethylene to a propylene polymerization system
has a dramatic and unexpectedly non-linear effect on the
productivity of these catalysts. Whereas the productivity of
ethylene polymerization at 25 psig (170 kPa) are in the range
3000-7280 kg polymer/mol Zr.hr (see Examples 67-71), surprisingly
the addition of 28 psig (190 kPa) of ethylene to a propylene
polymerization system derived from Catalyst D results in a
completely unexpected and significant 10-fold increase in
productivity at 20 C (6000 to 64,540 kg polymer/mol Zr.hr, Examples
38 and 39), clearly a non-linear effect. This means, inter alia,
that catalysts that were previously considered marginal or not
commrrercially of interest, can now be useful by using the PRE
process of this invention. Indeed, if they possess other good
properties, such catalysts that were formerly considered to be
impractical, can now be rendered superior to other hereto faster
catalysts by use in the EEF process of this invention.
The addition of ethylene into the polymerization systems of this
invention leads to ethylene incorporation into the polymer.
However, only an activity-enhancing amount of ethylene is required
to increase the polymerization activity while simultaneously
producing a high melting-temperature elastomeric polyolefin.
Examples 72-75 show elastomeric homopolymers of propylene with
excellent recovery properties (tensile set<12%) and stress
relaxation in the range of 38-40% (100% hysteresis test). As shown
in Examples 76-79, polymerization in the presence of only 1-2
weight % ethylene in the feed results in high polymerization
activity and yields polyolefin elastomers with useful elastomeric
properties, including melting points above 100.degree. C., tensile
set below 9% and stress relaxation in the range of 36-50%.
Moreover, as exemplified in Examples 80-85, a further aspect of the
invention is the surprising observation that by adding ethylene to
an unbridged fluxional metallocene polymerization system that would
normally produce a flexible but non-elastomeric polyolefin results
in an increase in polymerization activity and the production of
useful elastomeric polymers. Comparing Example 80 with Examples
81-83, and Example 84 with Example 85, the addition of small
amounts of ethylene to the polymerization increases the activity of
the catalyst. In all cases, the activity of the ethylene/propylene
copolymerization is higher than that of the homopolymerization in
the absence of ethylene. Propylene homopolymers made with catalysts
Q and S (Examples 80 and 84) exhibit yielding and drawing during
deformation. They deform non-uniformly by localized necking and
drawing during room temperature tensile tests at high deformation
rates. These materials can be designated "flexible non-elastomeric
thermoplastics" to distinguish them from "thermoplastic
elastomers". Tensile set after the first two hysteresis cycles at
100% elongation is above 39% (indicating very poor recovery
properties). Stress relaxation is also very high at greater than
60% as measured in the 5 minute stress relaxation test at 50%
elongation. Retained force in the second cycle of the 100%
elongation hysteresis test is zero. Thus, although the thermal
properties of the polymers are excellent (m.p.>140.degree. C.),
and they exhibit high elongations to break (600-800%), they are not
elastomeric.
Upon addition of a ethylene/propylene mixture to the activated
metallocenes Q and S, a new type of polymer is produced (Examples
81-83 and Example 85). These materials are clearly elastomeric in
nature: They deform uniformly to high elongations and exhibit high
recovery from elongation. The tensile set after the first
hysteresis cycle at 100% elongation is below 20% (in some cases
below 10%), indicating good recovery properties. Stress relaxation
at 50% elongation is below 55%. The retained force increases from 0
(in the homopolymer examples) to over 10% (in the copolymer
examples). In some cases, the retained force of the copolymers is
over 25% (with 50% retained force being the theoretical maximum).
Table 10 clearly shows that as the ethylene content of the
copolymers increase (from 0 to 4 mole %), the elastomeric
properties of the materials improve significantly. In addition,
even with ca. 4 mole % ethylene incorporation into the copolymer,
the melting points of these materials are greater than 100.degree.
C.
Industrial Applicability
It is clear that there is extensive industrial applicability for
the novel unbridged catalysts of this invention and the PRE effect
process of increasing reactivity by including small quantities of
ethylene in an olefin monomer reaction system to substantially
increase the rate of reaction and overall productivity to produce
high melting elastomers having excellent properties including those
produced by the EPE effect process.
It is also evident that the ligands of fluxional unbridged
catalysts of the present invention and percent ethylene in the feed
can be selected to tailor the properties of the polymers from
crystalline theromplastics to amorphous gum elastomers to
thermoplastic elastomers.
As is evident from the properties reported herein, the polymers
produced in fiber, film, sheet, molded, cast, or extruded product
form can be used in conjunction with or place of other polymers.
For example, thin film elastomeric ethylene, propylene or
copolymers of ethylene and propylene produced by the catalysts and
processes of this invention can be used whereever films which have
conforming, elastic, resilient or sealing properties are
needed.
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